Ikeda, Takashi; Uchida, Kenta; Matsuura, Yukiko; Takahashi, Hiroshi; Yoshida, Tsuyoshi; Kaji, Koichi; Koizumi, Itsuro
2016-01-01
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.
Diel activity patterns of the Louisiana pine snakes (Pituophis ruthveni) in eastern Texas
Marc J. Ealy; Robert R. Fleet; D. Craig Rudolph
2004-01-01
This study examined the diel activity patterns of six Louisiana pine snakes in eastern Texas using radio-telemetry. snakes were monitored for 44 days on two study areas from May to October 1996. Louisana pine snakes were primarily diurnal with moderate crepuscular activity, spending the night within pocket gopher burrows or inactive on the surface. During daylight...
NASA Astrophysics Data System (ADS)
Csabai, Zoltán; Kálmán, Zoltán; Szivák, Ildikó; Boda, Pál
2012-09-01
Dispersal flight is the most important and almost the only way for primary aquatic insects to find new water habitats. During a 30-week-long project, we monitored the flight dispersal behaviour of aquatic beetles and bugs with using highly and horizontally polarizing agricultural black plastic sheets laid onto the ground. Based on the flight data of more than 45,000 individuals and 92 species, we explored and described eight different diel flight activity patterns. We found that seven of eight dispersal patterns are consistent with the previous knowledge, while three conspicuous mass dispersal periods can be identified as in the mid morning and/or around noon and/or at nightfall. As an exception, we found a `daytime' pattern occurred exclusively in spring, in which mass dispersal can be seen from mid morning to late afternoon. In contrast to previous studies, we emphasize here that the seasonality has to be considered in evaluation of the diurnal flight activity. According to the seasons, a `three code sign' was proposed to indicate the diel dispersal flight behaviour of a species for a year. Most of the species utilize different diel activity patterns in different seasons. In spring, the daytime pattern was the preferred type, but in summer and autumn, the evening types were the most popular patterns. We stated that the seasonal change of air temperature has a crucial role in that a pattern could be manifested in a given season or not and brings a need to change the diel dispersal pattern among seasons.
Nocturnality in synapsids predates the origin of mammals by over 100 million years
Angielczyk, K. D.; Schmitz, L.
2014-01-01
Nocturnality is widespread among extant mammals and often considered the ancestral behavioural pattern for all mammals. However, mammals are nested within a larger clade, Synapsida, and non-mammalian synapsids comprise a rich phylogenetic, morphological and ecological diversity. Even though non-mammalian synapsids potentially could elucidate the early evolution of diel activity patterns and enrich the understanding of synapsid palaeobiology, data on their diel activity are currently unavailable. Using scleral ring and orbit dimensions, we demonstrate that nocturnal activity was not an innovation unique to mammals but a character that appeared much earlier in synapsid history, possibly several times independently. The 24 Carboniferous to Jurassic non-mammalian synapsid species in our sample featured eye morphologies consistent with all major diel activity patterns, with examples of nocturnality as old as the Late Carboniferous (ca 300 Ma). Carnivores such as Sphenacodon ferox and Dimetrodon milleri, but also the herbivorous cynodont Tritylodon longaevus were likely nocturnal, whereas most of the anomodont herbivores are reconstructed as diurnal. Recognizing the complexity of diel activity patterns in non-mammalian synapsids is an important step towards a more nuanced picture of the evolutionary history of behaviour in the synapsid clade. PMID:25186003
Patterns of Diel Variation in Nitrate Concentrations in the Potomac River
NASA Astrophysics Data System (ADS)
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 <1% of the mean daily NO3- concentration in winter and about 4% in summer; however, variation >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 of dispersion in obscuring diel patterns. Improvements to these diel estimates will require additional measures such as dissolved oxygen and ammonium, and the use of a second upstream measurement station to better constrain NO3- uptake values.
Nocturnality in synapsids predates the origin of mammals by over 100 million years.
Angielczyk, K D; Schmitz, L
2014-10-22
Nocturnality is widespread among extant mammals and often considered the ancestral behavioural pattern for all mammals. However, mammals are nested within a larger clade, Synapsida, and non-mammalian synapsids comprise a rich phylogenetic, morphological and ecological diversity. Even though non-mammalian synapsids potentially could elucidate the early evolution of diel activity patterns and enrich the understanding of synapsid palaeobiology, data on their diel activity are currently unavailable. Using scleral ring and orbit dimensions, we demonstrate that nocturnal activity was not an innovation unique to mammals but a character that appeared much earlier in synapsid history, possibly several times independently. The 24 Carboniferous to Jurassic non-mammalian synapsid species in our sample featured eye morphologies consistent with all major diel activity patterns, with examples of nocturnality as old as the Late Carboniferous (ca 300 Ma). Carnivores such as Sphenacodon ferox and Dimetrodon milleri, but also the herbivorous cynodont Tritylodon longaevus were likely nocturnal, whereas most of the anomodont herbivores are reconstructed as diurnal. Recognizing the complexity of diel activity patterns in non-mammalian synapsids is an important step towards a more nuanced picture of the evolutionary history of behaviour in the synapsid clade. © 2014 The Author(s) Published by the Royal Society. All rights reserved.
Patterns of diel variation in nitrate concentrations in the Potomac River
Burns, Douglas A.; Miller, Matthew P.; Pellerin, Brian; Capel, Paul D.
2016-01-01
The Potomac River is a large source of N to Chesapeake Bay, where reducing nutrient loads is a focus of efforts to improve trophic status. Better understanding of NO3– loss, reflected in part by diel variation in NO3– concentrations, may refine model predictions of N loads to the Bay. We analyzed 2 y of high-frequency NO3– sensor data in the Potomac to quantify seasonal variation in the magnitude and timing of diel NO3– loss. Diel patterns were evident, especially during low flow, despite broad seasonal and flow-driven variation in NO3– concentrations. Diel variation was ~0.01 mg N/L in winter and 0.02 to 0.03 mg N/L in summer with intermediate values in spring and autumn, equivalent to <1% of the daily mean NO3– concentration in winter and ~2 to 4% in summer. Maximum diel NO3– values generally occurred in mid- to late morning, with more repeatable patterns in summer and wider variation in autumn and winter. Diel NO3– loss reduced loads by 0.7% in winter and 3% in summer. These losses were less than estimates of total in-stream NO3– load loss across the basin that averaged 33% of the annual groundwater contribution to the river. Water temperature and discharge had stronger relationships to the daily magnitude of diel NO3– variation than did photosynthetically active radiation. Estimated diel areal NO3– loss rates were generally >1000 mg N m–2 d–1, greater than most published values because measurements in this large river integrate over a greater depth/unit stream bottom area than do those from smaller rivers. These diel NO3– patterns are consistent with the influence of photoautotrophic uptake and related denitrification, but we cannot attribute these patterns to assimilation alone because the magnitude and timing of diel dynamics were affected to an unknown extent by processes, such as evapotranspiration, transient storage, and hydrodynamic dispersion. Improvements to diel loss estimates will require additional high-frequency measures, such as dissolved O2, dissolved organic N, and NH4+, and deployment of 2 measurement stations.
Tewson, L H; Cowx, I G; Nunn, A D
2016-04-01
This study investigated diel variations in zooplankton composition and abundance, and the species composition, density, size structure, feeding activity, diet composition and prey selection of larval and 0+ year juvenile fishes in the littoral of a man-made floodplain waterbody over five 24 h periods within a 57 day period. There was a significant difference in the species composition of diurnal and nocturnal catches, with most species consistently peaking in abundance either during daylight or at night, reflecting their main activity period. There were no consistent diel patterns in assemblage structure or the abundance of some species, however, most likely, respectively, due to the phenology of fish hatching and ontogenetic shifts in diel behaviour or habitat use. There were few clear diel patterns in the diet composition or prey selection of larval and 0+ year juvenile roach Rutilus rutilus and perch Perca fluviatilis, with most taxa consistently selected or avoided irrespective of the time of day or night, and no obvious shift between planktonic and benthic food sources, but dietary overlap suggested that interspecific interactions were probably strongest at night. It is essential that sampling programmes account for the diel ecology of the target species, as diurnal surveys alone could produce inaccurate assessments of resource use. The relative lack of consistent diel patterns in this study suggests that multiple 24 h surveys are required in late spring and early summer to provide accurate assessments of 0+ year fish assemblage structure and foraging ecology. © 2016 The Fisheries Society of the British Isles.
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.
Zydlewski, Joseph D.; Coghlan, Stephen M.; Trial, Joan G.; Wathen, Gus
2012-01-01
Invasive smallmouth bass Micropterus dolomieu have been introduced to some of the last remaining watersheds that contain wild anadromous Atlantic salmon Salmo salar, yet little is known about the interactions between these species. We used an artificial stream equipped with passive integrated transponder tag antenna arrays to monitor habitat use and movements of age-0 Atlantic salmon and age-0 smallmouth bass in sympatry and allopatry. We used additive and substitutive designs to test for changes in habitat use, diel movements, and diel activity patterns of prior-resident Atlantic salmon or smallmouth bass resulting from the addition of conspecifics or heterospecifics. Atlantic salmon prior residents did not change their habitat use in the presence of conspecific or heterospecific invaders. However, Atlantic salmon invaders did lessen riffle habitat use by smallmouth bass prior residents during daytime. Atlantic salmon and smallmouth bass displayed different diel activity patterns of movement (Atlantic salmon were more nocturnal; smallmouth bass were more diurnal), which were affected by heterospecific introductions. Because the two species tended to favor different habitat types and displayed different diel activity patterns, we suggest that under the conditions tested, the level of interspecific competition for habitat was low. Age-0 Atlantic salmon and smallmouth bass may be able to avoid intense interspecific competition through spatial and temporal habitat partitioning. These data do not, however, predict the potential for competition under different seasonal or ontogenetic circumstances.
Application of activity sensors for estimating behavioral patterns
Roberts, Caleb P.; Cain, James W.; Cox, Robert D.
2016-01-01
The increasing use of Global Positioning System (GPS) collars in habitat selection studies provides large numbers of precise location data points with reduced field effort. However, inclusion of activity sensors in many GPS collars also grants the potential to remotely estimate behavioral state. Thus, only using GPS collars to collect location data belies their full capabilities. Coupling behavioral state with location data would allow researchers and managers to refine habitat selection models by using diel behavioral state changes to partition fine-scale temporal shifts in habitat selection. We tested the capability of relatively unsophisticated GPS-collar activity sensors to estimate behavior throughout diel periods using free-ranging female elk (Cervus canadensis) in the Jemez Mountains of north-central New Mexico, USA, 2013–2014. Collars recorded cumulative number of movements (hits) per 15-min recording period immediately preceding GPS fixes at 0000, 0600, 1200, and 1800 hr. We measured diel behavioral patterns of focal elk, categorizing active (i.e., foraging, traveling, vigilant, grooming) and inactive (i.e., resting) states. Active behaviors (foraging, traveling) produced more average hits (0.87 ± 0.69 hits/min, 4.0 ± 2.2 hits/min, respectively; 95% CI) and inactive (resting) behavior fewer hits (−1.1 ± 0.61 95% CI). We differentiated active and inactive behavioral states with a bootstrapped threshold of 5.9 ± 3.9 hits/15-min recording period. Mean cumulative activity-sensor hits corresponded with observed diel behavioral patterns: hits increased during crepuscular (0600, 1800 hr) observations when elk were most active (0000–0600 hr: d = 0.19; 1200–1800 hr: d = 0.64) and decreased during midday and night (0000 hr, 1200 hr) when elk were least active (1800–0000 hr: d = −0.39; 0600–1200 hr: d = −0.43). Even using relatively unsophisticated GPS-collar activity sensors, managers can remotely estimate behavioral states, approximate diel behavioral patterns, and potentially complement location data in developing habitat selection models.
Temporal Links in Daily Activity Patterns between Coral Reef Predators and Their Prey
Bosiger, Yoland J.; McCormick, Mark I.
2014-01-01
Few studies have documented the activity patterns of both predators and their common prey over 24 h diel cycles. This study documents the temporal periodicity of two common resident predators of juvenile reef fishes, Cephalopholis cyanostigma (rockcod) and Pseudochromis fuscus (dottyback) and compares these to the activity and foraging pattern of a common prey species, juvenile Pomacentrus moluccensis (lemon damselfish). Detailed observations of activity in the field and using 24 h infrared video in the laboratory revealed that the two predators had very different activity patterns. C. cyanostigma was active over the whole 24 h period, with a peak in feeding strikes at dusk and increased activity at both dawn and dusk, while P. fuscus was not active at night and had its highest strike rates at midday. The activity and foraging pattern of P. moluccensis directly opposes that of C. cyanostigma with individuals reducing strike rate and intraspecific aggression at both dawn and dusk, and reducing distance from shelter and boldness at dusk only. Juveniles examined were just outside the size-selection window of P. fuscus. We suggest that the relatively predictable diel behaviour of coral reef predators results from physiological factors such as visual sensory abilities, circadian rhythmicity, variation in hunting profitability, and predation risk at different times of the day. Our study suggests that the diel periodicity of P. moluccensis behaviour may represent a response to increased predation risk at times when both the ability to efficiently capture food and visually detect predators is reduced. PMID:25354096
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.
Tarlow, Elisa M; Hau, Michaela; Anderson, David J; Wikelski, Martin
2003-10-01
We investigated the effects of moon phases and age on diel rhythms of plasma melatonin and corticosterone in free-living Nazca boobies (Sula granti) on the Galápagos Islands, Ecuador. Melatonin and corticosterone secretion are regulated by the circadian system and the two hormones play a role in the control of locomotor activity and foraging, which can be influenced by moon phases. These seabirds have a long life span and in many vertebrates circadian function deteriorates with age. The functioning of the circadian system under different environmental conditions and changes related to age are poorly understood and hardly studied in wild birds. Nazca boobies had generally low plasma melatonin concentrations but showed a diel variation with higher concentrations at 00:00 and 16:00h. The diel variations in melatonin concentrations disappeared during full moon, suggesting that natural light levels at night can suppress melatonin secretion in Nazca boobies. Maximal melatonin concentrations tended to decline in older birds (10-19 years). Birds showed a clear diel variation in basal plasma corticosterone with a peak in the early morning, before the active period begins, and low concentrations throughout the day. As with melatonin, there were no diel variations in corticosterone at full moon, which may be due to different activity patterns in response to food availability or changes in the circadian system. While other studies have found a relationship between corticosterone and melatonin, we found no such correlation in Nazca boobies. The lunar cycle appears to affect the hormone titers of Nazca boobies both directly and indirectly. First, melatonin rhythms can be directly affected by the light intensity associated with full moon. Second, prey availability may change foraging patterns and can therefore indirectly alter corticosterone secretion in Nazca boobies.
Louyakis, Artemis S; Gourlé, Hadrien; Casaburi, Giorgio; Bonjawo, Rachelle M E; Duscher, Alexandrea A; Foster, Jamie S
2018-02-01
Microbialites are one of the oldest known ecosystems on Earth and the coordinated metabolisms and activities of these mineral-depositing communities have had a profound impact on the habitability of the planet. Despite efforts to understand the diversity and metabolic potential of these systems, there has not been a systematic molecular analysis of the transcriptional changes that occur within a living microbialite over time. In this study, we generated metatranscriptomic libraries from actively growing thrombolites, a type of microbialite, throughout diel and seasonal cycles and observed dynamic shifts in the population and metabolic transcriptional activity. The most transcribed genes in all seasons were associated with photosynthesis, but only transcripts associated with photosystem II exhibited diel cycling. Photosystem I transcripts were constitutively expressed at all time points including midnight and sunrise. Transcripts associated with nitrogen fixation, methanogenesis and dissimilatory sulfate reduction exhibited diel cycling, and variability between seasons. Networking analysis of the metatranscriptomes showed correlated expression patterns helping to elucidate how metabolic interactions are coordinated within the thrombolite community. These findings have identified distinctive temporal patterns within the thrombolites and will serve an important foundation to understand the mechanisms by which these communities form and respond to changes in their environment. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.
Aldinger, Joni L.; Welsh, Stuart A.
2017-01-01
Yellow-phase American eel (Anguilla rostrata) upstream migration is temporally punctuated, yet migration chronology within diel time periods is not well-understood. This study examined diel periodicity, chronology, and total length (TL) of six multi-day, high-count (285–1,868 eels) passage events of upstream migrant yellow-phase American eels at the Millville Dam eel ladder, lower Shenandoah River, West Virginia during 2011–2014. We categorized passage by diel periods (vespertine, nocturnal, matutinal, diurnal) and season (spring, summer, late summer/early fall, fall). We depicted passage counts as time-series histograms and used time-series spectral analysis (Fast Fourier Transformation) to identify cyclical patterns and diel periodicity of upstream migration. We created histograms to examine movement patterns within diel periods for each passage event and fit normal mixture models (2–9 mixtures) to describe multiple peaks of passage counts. Periodicity of movements for each passage event followed a 24-h activity cycle with mostly nocturnal movement. Multimodal models were supported by the data; most modes represented nocturnal movements, but modes at or near the transition between twilight and night were also common. We used mixed-model methodology to examine relationships among TL, diel period, and season. An additive-effects model of diel period + season was the best approximating model. A decreasing trend of mean TL occurred across diel movement periods, with the highest mean TL occurring during fall relative to similar mean values of TL for spring, summer, and late summer/early fall. This study increased our understanding of yellow-phase American eels by demonstrating the non-random nature of their upstream migration.
Do larval fishes exhibit diel drift patterns in a large, turbid river?
Reeves, K.S.; Galat, D.L.
2010-01-01
Previous research suggested larval fishes do not exhibit a diel drift cycle in turbid rivers (transparency <30 cm). We evaluated this hypothesis in the turbid, lower Missouri River, Missouri. We also reviewed diel patterns of larval drift over a range of transparencies in rivers worldwide. Larval fishes were collected from the Missouri River primary channel every 4 h per 24-h period during spring-summer 2002. Water transparency was measured during this period and summarized for previous years. Diel drift patterns were analyzed at the assemblage level and lower taxonomic levels for abundant groups. Day and night larval fish catch-per-unit-effort (CPUE) was compared for the entire May through August sampling period and spring (May - June) and summer (July - August) seasons separately. There were no significant differences between day and night CPUE at the assemblage level for the entire sampling period or for the spring and summer seasons. However, Hiodon alosoides, Carpiodes/Ictiobus spp. and Macrhybopsis spp. exhibited a diel cycle of abundance within the drift. This pattern was evident although mean Secchi depth (transparency) ranged from 4 to 25 cm during the study and was <30 cm from May through August over the previous nine years. Larval diel drift studies from 48 rivers excluding the Missouri River indicated the primary drift period for larval fishes was at night in 38 rivers and during the day for five, with the remaining rivers showing no pattern. Water transparency was reported for 10 rivers with six being <30 cm or 'low'. Two of these six turbid rivers exhibited significant diel drift patterns. The effect of water transparency on diel drift of larval fishes appears taxa-specific and patterns of abundant taxa could mask patterns of rare taxa when analyzed only at the assemblage level. ?? 2010 Blackwell Verlag, Berlin.
NASA Astrophysics Data System (ADS)
Vislova, A.; Aylward, F.; Sosa, O.; DeLong, E.
2016-02-01
Previous work has revealed diel periodicity of gene expression in key metabolic pathways in both autotrophic and heterotrophic microbes in the surface ocean. In this study, we investigated patterns of diel periodicity of gene expression in depth profiles (25, 75, 125 and 250 meters). We postulated that microbial diel transcriptional signals would be increasingly dampened with depth, and that the timing of peak expression of specific transcripts would be shifted in time between depths, in accordance with depth-dependent diel light variability. Bacterioplankton were sampled from four depths every four hours at station ALOHA (22° 45' N 158° W) over 2 days. RNA was extracted from cells preserved on filters, converted to cDNA, and sequenced on the Illumina platform. Surprisingly, harmonic regression analysis revealed an increasing proportion of genes with diel periodic expression patterns with increasing depth between 25- 125 meters. At 250 meters, the proportion of genes exhibiting diel expression patterns decreased an order of magnitude compared to the photic zone. Community composition, functional gene categories, and diel patterns of gene expression were significantly different between the photic zone and 250 meter samples. The signals driving diel periodic gene expression in microbes at 250 meters is under further investigation. These data are now beginning provide a better understanding of the tempo and mode of microbial dynamics among specific taxa, throughout the ocean's interior.
USDA-ARS?s Scientific Manuscript database
Knowledge of daily activity patterns in adult mosquitoes can be used to determine the best time to apply adulticides for mosquito control. Many factors influence these activity patterns, including migration, hormonal cycles in the mosquito, hunger, and the need to lay eggs. In this study, FL scien...
Circadian Clock Gene Expression in the Coral Favia fragum over Diel and Lunar Reproductive Cycles
Hoadley, Kenneth D.; Szmant, Alina M.; Pyott, Sonja J.
2011-01-01
Natural light cycles synchronize behavioral and physiological cycles over varying time periods in both plants and animals. Many scleractinian corals exhibit diel cycles of polyp expansion and contraction entrained by diel sunlight patterns, and monthly cycles of spawning or planulation that correspond to lunar moonlight cycles. The molecular mechanisms for regulating such cycles are poorly understood. In this study, we identified four molecular clock genes (cry1, cry2, clock and cycle) in the scleractinian coral, Favia fragum, and investigated patterns of gene expression hypothesized to be involved in the corals' diel polyp behavior and lunar reproductive cycles. Using quantitative PCR, we measured fluctuations in expression of these clock genes over both diel and monthly spawning timeframes. Additionally, we assayed gene expression and polyp expansion-contraction behavior in experimental corals in normal light:dark (control) or constant dark treatments. Well-defined and reproducible diel patterns in cry1, cry2, and clock expression were observed in both field-collected and the experimental colonies maintained under control light:dark conditions, but no pattern was observed for cycle. Colonies in the control light:dark treatment also displayed diel rhythms of tentacle expansion and contraction. Experimental colonies in the constant dark treatment lost diel patterns in cry1, cry2, and clock expression and displayed a diminished and less synchronous pattern of tentacle expansion and contraction. We observed no pattern in cry1, cry2, clock, or cycle expression correlated with monthly spawning events suggesting these genes are not involved in the entrainment of reproductive cycles to lunar light cycles in F. fragum. Our results suggest a molecular clock mechanism, potentially similar to that in described in fruit flies, exists within F. fragum. PMID:21573070
Diel stream temperature regimes of Bukovsky regions of the conterminous United States
NASA Astrophysics Data System (ADS)
Ferencz, Stephen B.; Cardenas, M. Bayani
2017-03-01
Stream temperature which varies over daily to seasonal timescales is a primary control on myriad ecological, biogeochemical, and physical processes. Yet geographic patterns of its diel variations have not been fully characterized. Using daily temperature records spanning 15 years (2000-2014), monthly averaged mean daily temperature and diel temperature range were calculated for streams distributed across six Bukovsky regions of the conterminous U.S. Across all six regions, diel temperature fluctuations were lowest during the winter, around 1-2°C. During the summer there was wide distribution in diel temperatures (2°C-12°C). The regions revealed distinct differences in diel patterns for small and medium streams, but not for large streams. Small and medium streams exhibited notable hysteresis in their annual progression of diel temperature ranges, with larger diel temperature fluctuations in the spring than in the fall.
NASA Astrophysics Data System (ADS)
Primo, Ana Lígia; Azeiteiro, Ulisses M.; Marques, Sónia C.; Ré, Pedro; Pardal, Miguel A.
2012-07-01
Vertical distribution and migration pattern of ichthyoplankton assemblage in the Mondego estuary were investigated in relation to diel and tidal cycle. Summer and winter communities were sampled, at surface and bottom, over a diel cycle during spring and neap tides at a fixed station at the mouth of the estuary. Summer presented higher larvae density mainly of Pomatoschistus spp., Gobius niger and Parablennius pilicornis. Main species in winter assemblages were Pomatoschistus spp. and Sardina pilchardus. There were no differences between depth stratums across diel or tide cycle. Nevertheless, main species larval densities showed significant periodic variation associated with tide (M2) and diel (K1) cycles presenting generally, higher density at night and around low tide. Conversely, vertical patterns observed could not be related with diel or tidal cycle. Tough, main species presented some extent of vertical migration. Vertical patterns observed appear to be related to seasonal stratification and river flow, increasing amplitude during periods of less stratification and lower water currents. Present study provides a better understanding of ichthyoplankton vertical movement patterns and of small scale dynamics at the interface of two coastal European systems.
NASA Astrophysics Data System (ADS)
Brickman, Jon; Tanchez, Erin; Thomas, Jeanette
2005-09-01
Diel patterns in underwater sounds from five beluga whales (Delphinapterus leucas) and five Pacific white-sided dolphins (Lagenorhynchus obliquidens) housed at John G. Shedd Aquarium in Chicago, IL were studied. Underwater sounds were sampled systematically over 24-h periods by using a battery-operated cassette recorder and an Ithaco 605C hydrophone controlled by a digital timer, which activated every hour and then shut off after 2.5 min. Belugas had 14 sounds and Pacific white-sided dolphins produced 5 sounds. For each species, the use of some sounds was correlated with other sounds. The diel pattern for both species was similar and mostly affected by the presence of humans. Sounds gradually increased after the staff and visitors arrived, peaked during the midday, gradually decreased as closing of the aquarium approached, and was minimal overnight. These data can help identify the best time of day to make recordings and perhaps could be used to examine social, reproductive, or health changes in these captive cetaceans.
Diel Patterns of Activity for Insect Pollinators of Two Oil Palm Species (Arecales : Arecaceae)
Frérot, Brigitte; Poveda, Roberto; Louise, Claude; Beaudoin-Ollivier, Laurence
2017-01-01
The pollination of two oil palm species, Elaeis guineensis Jacquin and Elaeis oleifera Cortés (Arecales: Arecaceae), depends on a mutualistic relation with insects, which use male inflorescences as a brood site, and visits female inflorescences lured by the emitted odor, which is similar to that of males. Although the activity of visiting the inflorescences by these insects is critical for the adequate natural pollination of the host plant, their activity is poorly documented. In the present study, we determine the diel activity of two specialized pollinator weevils (Coleoptera: Curculionidae) on inflorescences of their respective host-palm: Elaeidobius kamerunicus Faust specialized on E. guineensis, and Grasidius hybridus O’Brien and Beserra specialized on E. oleifera. The average timing of activity was studied by using passive interception traps. Then the pattern and the duration were refined by using aspiration trapping within the active period for each insect species at the male and female inflorescences. All the experiments were conducted in an Ecuadorian oil palm plantation, located close to Amazonian forest. El. kamerunicus and G. hybridus were found to be the pollinators of E. guineensis and E. oleifera, respectively. The two species differed in their diel pattern of activity: E. kamerunicus was active in the morning and G. hybridus during a short period at dusk. For both palm species, insect visits were synchronous on both male and female inflorescences. The synchronicity is discussed as a strategy to maintain the relation mutualistic between partners. These findings increase our understanding of the oil palm pollination system. PMID:28365767
NASA Astrophysics Data System (ADS)
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.
Diel growth dynamics in tree stems: linking anatomy and ecophysiology.
Steppe, Kathy; Sterck, Frank; Deslauriers, Annie
2015-06-01
Impacts of climate on stem growth in trees are studied in anatomical, ecophysiological, and ecological disciplines, but an integrative framework to assess those impacts remains lacking. In this opinion article, we argue that three research efforts are required to provide that integration. First, we need to identify the missing links in diel patterns in stem diameter and stem growth and relate those patterns to the underlying mechanisms that control water and carbon balance. Second, we should focus on the understudied mechanisms responsible for seasonal impacts on such diel patterns. Third, information on stem anatomy and ecophysiology should be integrated in the same experiments and mechanistic plant growth models to capture both diel and seasonal scales. Copyright © 2015 Elsevier Ltd. All rights reserved.
Nico, Leo G.
2010-01-01
Several Pterygoplichthys species, members of the Neotropical catfish family Loricariidae, have been widely introduced outside their native ranges. In this paper, I present observations on the diel activity pattern of non-native Pterygoplichthys, tentatively identified as P. disjunctivus, with respect to their attachment and grazing on endangered Florida manatees, Trichechus manatus latirostris. The study was conducted in December 2009 at Volusia Blue Spring, an artesianal spring system in the St. Johns River basin, Florida (USA). Supplemented by information gathered during previous visits to the spring site, this study revealed that adult Pterygoplichthys are active throughout the diel period (day, twilight and night). However, juvenile Pterygoplichthys were largely nocturnal and only at night did they consistently join adults in attaching to manatees. The juveniles generally remain hidden during the day, probably responding to presence of diurnal predators, mainly birds. Differences in diel behaviors among different Pterygoplichthys size classes in Florida are consistent with published observations on loricariids inhabiting clearwater streams within their native ranges.
Volkmar, E.C.; Dahlgren, R.A.; Stringfellow, W.T.; Henson, S.S.; Borglin, S.E.; Kendall, C.; Van Nieuwenhuyse, E. E.
2011-01-01
To investigate the mechanism for diel (24h) changes commonly observed at fixed sampling locations and how these diel changes relate to downstream transport in hypereutrophic surface waters, we studied a parcel of agricultural drainage water as it traveled for 84h in a concrete-lined channel having no additional water inputs or outputs. Algal fluorescence, dissolved oxygen, temperature, pH, conductivity, and turbidity were measured every 30min. Grab samples were collected every 2h for water quality analyses, including nutrients, suspended sediment, and chlorophyll/pheophytin. Strong diel patterns were observed for dissolved oxygen, pH, and temperature within the parcel of water. In contrast, algal pigments and nitrate did not exhibit diel patterns within the parcel of water, but did exhibit strong diel patterns for samples collected at a fixed sampling location. The diel patterns observed at fixed sampling locations for these constituents can be attributed to algal growth during the day and downstream transport (washout) of algae at night. Algal pigments showed a rapid daytime increase during the first 48h followed by a general decrease for the remainder of the study, possibly due to sedimentation and photobleaching. Algal growth (primarily diatoms) was apparent each day during the study, as measured by increasing dissolved oxygen concentrations, despite low phosphate concentrations (<0.01mgL-1). ?? 2011 Elsevier B.V.
Straight, Carrie A.; Jackson, C. Rhett; Freeman, Byron J.; Freeman, Mary C.
2015-01-01
The conservation of imperiled species depends upon understanding threats to the species at each stage of its life history. In the case of many imperiled migratory fishes, understanding how timing and environmental influences affect reproductive behavior could provide managers with information critical for species conservation. We used passive acoustic recorders to document spawning activities for two large-bodied catostomids (Robust Redhorse Moxostoma robustum in the Savannah and Broad rivers, Georgia, and River Redhorse M. carinatum in the Coosawattee River, Georgia) in relation to time of day, water temperature, discharge variation, moonlight, and weather. Robust Redhorse spawning activities in the Savannah and Broad rivers were more frequent at night or in the early morning (0100–0400 hours and 0800–1000 hours, respectively) and less frequent near midday (1300 hours). Spawning attempts in the Savannah and Broad rivers increased over a 3–4-d period and then declined. River Redhorse spawning activities in the Coosawattee River peaked on the first day of recording and declined over four subsequent days; diel patterns were less discernible, although moon illumination was positively associated with spawning rates, which was also observed for Robust Redhorses in the Savannah River. Spawning activity in the Savannah and Broad rivers was negatively associated with water temperature, and spawning activity increased in association with cloud cover in the Savannah River. A large variation in discharge was only measured in the flow-regulated Savannah River and was not associated with spawning attempts. To our knowledge, this is the first study to show diel and multiday patterns in spawning activities for anyMoxostoma species. These patterns and relationships between the environment and spawning activities could provide important information for the management of these species downstream of hydropower facilities.
USDA-ARS?s Scientific Manuscript database
Temporal patterns of landing activity on a human host by female Anopheles quadrimaculatus, Culex nigripalpus, Cx. quinquefasciatus, Ochlerotatus triseriatus and Aedes albopictus varied significantly throughout the diel period and with respect to time of collection within a 15 minute observation peri...
Queiroz, Nuno; Humphries, Nicolas E.; Noble, Leslie R.; Santos, António M.; Sims, David W.
2012-01-01
Dramatic population declines among species of pelagic shark as a result of overfishing have been reported, with some species now at a fraction of their historical biomass. Advanced telemetry techniques enable tracking of spatial dynamics and behaviour, providing fundamental information on habitat preferences of threatened species to aid conservation. We tracked movements of the highest pelagic fisheries by-catch species, the blue shark Prionace glauca, in the North-east Atlantic using pop-off satellite-linked archival tags to determine the degree of space use linked to habitat and to examine vertical niche. Overall, blue sharks moved south-west of tagging sites (English Channel; southern Portugal), exhibiting pronounced site fidelity correlated with localized productive frontal areas, with estimated space-use patterns being significantly different from that of random walks. Tracked female sharks displayed behavioural variability in diel depth preferences, both within and between individuals. Diel depth use ranged from normal DVM (nDVM; dawn descent, dusk ascent), to reverse DVM (rDVM; dawn ascent, dusk descent), to behavioural patterns where no diel differences were apparent. Results showed that blue sharks occupy some of the most productive marine zones for extended periods and structure diel activity patterns across multiple spatio-temporal scales in response to particular habitat types. In so doing, sharks occupied an extraordinarily broad vertical depth range for their size (1.0–2.0 m fork length), from the surface into the bathypelagic realm (max. dive depth, 1160 m). The space-use patterns of blue sharks indicated they spend much of the time in areas where pelagic longlining activities are often highest, and in depth zones where these fisheries particularly target other species, which could account for the rapid declines recently reported for blue sharks in many parts of the world's oceans. Our results provide habitat targets for blue shark conservation that may also be relevant to other pelagic species. PMID:22393403
Seasonal and diel patterns in cetacean use and foraging at a potential marine renewable energy site.
Nuuttila, Hanna K; Bertelli, Chiara M; Mendzil, Anouska; Dearle, Nessa
2018-04-01
Marine renewable energy (MRE) developments often coincide with sites frequented by small cetaceans. To understand habitat use and assess potential impact from development, echolocation clicks were recorded with acoustic click loggers (C-PODs) in Swansea Bay, Wales (UK). General Additive Models (GAMs) were applied to assess the effects of covariates including month, hour, tidal range and temperature. Analysis of inter-click intervals allowed the identification of potential foraging events as well as patterns of presence and absence. Data revealed year-round presence of porpoise, with distinct seasonal and diel patterns. Occasional acoustic encounters of dolphins were also recorded. This study provides further evidence of the need for assessing temporal trends in cetacean presence and habitat use in areas considered for development. These findings could assist MRE companies to monitor and mitigate against disturbance from construction, operation and decommissioning activities by avoiding times when porpoise presence and foraging activity is highest in the area. Copyright © 2017 Elsevier Ltd. All rights reserved.
Gorman, O.T.; Yule, D.L.; Stockwell, J.D.
2012-01-01
Diel patterns of distribution of fishes in nearshore (15–80 m depth) and offshore (>80 m) waters of the Apostle Islands region of Lake Superior were described using bottom trawls, mid-water trawls, and acoustic gear during day and night sampling. These data revealed three types of diel migration: diel vertical migration (DVM), diel bank migration (DBM), and no migration. DVM was expressed by fishes migrating from benthopelagic to pelagic strata and DBM was expressed by fishes migrating horizontally from deeper waters in the day to shallower waters at night while remaining within the benthopelagic stratum. Most fishes that did not exhibit diel migration showed increased nighttime densities as a result of increased activity and movement from benthic to benthopelagic strata. Rainbow Smelt (Osmerus mordax), Cisco (Coregonus artedi), Bloater (C. hoyi), Kiyi (C. kiyi), juvenile Trout-Perch (Percopsis omiscomaycus), and adult siscowet (Salvelinus namaycush siscowet) exhibited DVM. Lake Whitefish (C. clupeaformis), lean Lake Trout (Salvelinus namaycush namaycush), and juvenile siscowet exhibited DBM. Adult Trout-Perch and adult Pygmy Whitefish (Prosopium coulteri) exhibited a mixture of DBM and DVM. Burbot (Lota lota), Slimy Sculpin (Cottus cognatus), Spoonhead Sculpin (C. ricei), and Deepwater Sculpin (Myoxocephalus thompsonii) did not exhibit diel migration, but showed evidence of increased nocturnal activity. Ninespine Stickleback (Pungitius pungitius) exhibited a mixture of DVM and non-migration. Juvenile Pygmy Whitefish did not show a diel change in density or depth distribution. Species showing ontogenetic shifts in depth distribution with larger, adult life stages occupying deeper waters included, Rainbow Smelt, lean and siscowet Lake Trout, Lake Whitefish, Pygmy Whitefish, Ninespine Stickleback and Trout-Perch. Of these species, siscowet also showed an ontogenetic shift from primarily DBM as juveniles to primarily DVM as adults. Across all depths, fishes expressing DVM accounted for 73% of the total estimated community areal biomass (kg ha−1) while those expressing DBM accounted for 25% and non-migratory species represented 2% of the biomass. The proportion of total community biomass exhibiting DVM increased with depth, from 59% to 95% across ≤30 m to >90 m depth zones. Along the same depth gradient, the proportion of total community biomass exhibiting DBM declined from 40% to 1%, while non-migrators increased from 1% to 4%. These results indicate that DVM and DBM behaviors are pervasive in the Lake Superior fish community and potentially provide strong linkages that effect coupling of benthic and pelagic and nearshore and offshore habitats.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Brooks, Scott C.; Lowe, Kenneth Alan
We conducted a diel sampling campaign at three locations along the Hg contaminated East Fork Poplar Creek (EFPC) in Oak Ridge, Tennessee to (i) quantify diel patterns of particulate and dissolved mercury (Hg) and monomethylmercury (MMHg) (HgD, HgP, MMHgD, and MMHgP, respectively) and associated water quality parameters along a longitudinal gradient of EFPC during the summer season, (ii) determine if diel patterns in Hg and/or MMHg are related to the daily photocycle or any other short term cycle, such as wastewater treatment plant discharge, (iii) determine if diel variability in turbidity and dissolved organic matter (DOM) composition correspond to particulatemore » HgP or MMHgP and dissolved organic carbon (DOC) or dissolved HgD or MMHgD. Samples were collected every two hours for a 30 hour period. The farthest upstream site was located at the boundary of Y-12 and the City of Oak Ridge (EFK 23.4) while two additional sites were located 7.2 kilometers (Wiltshire Drive, EFK 16.2) and 18 kilometers (Horizon Center, EFK 5.4) downstream of EFK 23.4).HgP and MMHgP concentrations increased overnight at EFK 16.2 and EFK 5.4 coincident with increases in turbidity and total suspended solids (TSS). These overnight increases were likely due to diel changes in the activity of macrobiota (re)suspending contaminated sediments in the creek. Both HgD and MMHgD were higher during the day at EFK 23.4 and EFK 5.4. The underlying causes for the patterns in HgD and MMHgD are less clear but correspond with similar patterns in DOC concentration and DOM composition. Photochemical reactions may also play a role in these HgD, MMHgD, DOC, and DOM patterns. Both Hg and MMHg loading increased with downstream distance. The greatest increase in loading occurred in the reach from EFK 23.4 to EFK 16.2 which encompasses areas where the Historic Release Deposits (HRD) have been identified. These results suggest that diffuse legacy sources of Hg, outside of Y-12, contribute Hg load to EFPC whereas MMHg is generated from instream processes.Intraday patterns in Hg and MMHg concentration and speciation have implications with respect to biotic exposure. Greater biotic activity and feeding during times of higher concentration would correspond to greater exposure than estimated from daily or longer term averages. Both Hg and MMHg responded rapidly to processes governing their concentration. This latter point is encouraging from the perspective of site remediation as it suggests that MMHg concentrations and flux in EFPC would respond rapidly to appropriate remedial actions.« less
Absence of consistent diel rhythmicity in mated honey bee queen behavior.
Johnson, Jennifer N; Hardgrave, Emily; Gill, Curtis; Moore, Darrell
2010-07-01
Relatively little is known about the temporal control of behavior of honey bee queens under natural conditions. To determine if mated honey bee queens possess diel rhythmicity in behavior, we observed them in glass-sided observation hives, employing two focal studies involving continuous observations of individual queens as well as a scan-sampling study of multiple queens. In all cases, all behaviors were observed at all times of the day and night. In four of the five queens examined in focal studies, there were no consistent occurrences of diel periodicity for any of the individual behaviors. A more encompassing measure for periodicity, in which the behaviors were characterized as active (walking, inspecting, egg-laying, begging for food, feeding, and grooming self) or inactive (standing), also failed to reveal consistent diel rhythmicity. Furthermore, there were no consistent diel differences in the number of workers in the queen's retinue. Behavioral arrhythmicity persisted across seasons and despite daily changes in both light and temperature levels. Both day and night levels of behavioral activity were correlated with daytime, but not with nighttime, ambient temperatures. The behavior of the one exceptional queen was not consistent: diurnal activity patterns were present during two 24-h observation sessions but arrhythmicity during another. Based on the behavior observed by all but one of the queens examined in this work, the arrhythmic behavior by the mated honey bee queen inside the colony appears to be similar to that exhibited by worker bees before they approach the age of onset of foraging behavior. Copyright 2010 Elsevier Ltd. All rights reserved.
Wang, Zhi-Tao; Nachtigall, Paul E; Akamatsu, Tomonari; Wang, Ke-Xiong; Wu, Yu-Ping; Liu, Jian-Chang; Duan, Guo-Qin; Cao, Han-Jiang; Wang, Ding
2015-01-01
A growing demand for sustainable energy has led to an increase in construction of offshore windfarms. Guishan windmill farm will be constructed in the Pearl River Estuary, China, which sustains the world's largest known population of Indo-Pacific humpback dolphins (Sousa chinensis). Dolphin conservation is an urgent issue in this region. By using passive acoustic monitoring, a baseline distribution of data on this species in the Pearl River Estuary during pre-construction period had been collected. Dolphin biosonar detection and its diel, lunar, seasonal and tidal patterns were examined using a Generalized Linear Model. Significant higher echolocation detections at night than during the day, in winter-spring than in summer-autumn, at high tide than at flood tide were recognized. Significant higher echolocation detections during the new moon were recognized at night time. The diel, lunar and seasonal patterns for the echolocation encounter duration also significantly varied. These patterns could be due to the spatial-temporal variability of dolphin prey and illumination conditions. The baseline information will be useful for driving further effective action on the conservation of this species and in facilitating later assessments of the effects of the offshore windfarm on the dolphins by comparing the baseline to post construction and post mitigation efforts.
Wang, Zhi-Tao; Nachtigall, Paul E.; Akamatsu, Tomonari; Wang, Ke-Xiong; Wu, Yu-Ping; Liu, Jian-Chang; Duan, Guo-Qin; Cao, Han-Jiang; Wang, Ding
2015-01-01
A growing demand for sustainable energy has led to an increase in construction of offshore windfarms. Guishan windmill farm will be constructed in the Pearl River Estuary, China, which sustains the world’s largest known population of Indo-Pacific humpback dolphins (Sousa chinensis). Dolphin conservation is an urgent issue in this region. By using passive acoustic monitoring, a baseline distribution of data on this species in the Pearl River Estuary during pre-construction period had been collected. Dolphin biosonar detection and its diel, lunar, seasonal and tidal patterns were examined using a Generalized Linear Model. Significant higher echolocation detections at night than during the day, in winter-spring than in summer-autumn, at high tide than at flood tide were recognized. Significant higher echolocation detections during the new moon were recognized at night time. The diel, lunar and seasonal patterns for the echolocation encounter duration also significantly varied. These patterns could be due to the spatial-temporal variability of dolphin prey and illumination conditions. The baseline information will be useful for driving further effective action on the conservation of this species and in facilitating later assessments of the effects of the offshore windfarm on the dolphins by comparing the baseline to post construction and post mitigation efforts. PMID:26580966
Diel activity of Gulf of Mexico sturgeon in a northwest Florida bay
Wrege, B.M.; Duncan, M.S.; Isely, J.J.
2011-01-01
In this paper, we assess patterns in activity of Gulf of Mexico sturgeon Acipenser oxyrinchus desotoi over a 24-h period in the Pensacola bay system, Florida. Although seasonal migration of sturgeon is well documented, little information is available pertaining to daily variation in activity. We surgically implanted 58 Gulf sturgeon with acoustic transmitters in the Escambia (n=26), Yellow (n=8), Blackwater (n=12) and Choctawhatchee rivers (n=12) in June, July, September and October 2005. Gulf sturgeon location was monitored using an array of 56 fixed-station acoustic receivers. The relationship between frequency of Gulf sturgeon observations recorded on all acoustic receivers and time of day for all seasons combined indicated a strong diel activity pattern. Gulf sturgeon were frequently detected at night in all seasons with the exception of summer. Consecutive hourly observations indicated lateral movement of Gulf sturgeon between independent acoustic receivers on 15% of all observations of individuals. The use of an acoustic receiver array not only provides continuous data within a defined area, but also provides insight into nocturnal behavior of Gulf sturgeon not previously identified. ?? 2011 Blackwell Verlag, Berlin.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Roberts, Brian J; Mulholland, Patrick J
2007-01-01
A growing body of evidence demonstrates the importance of in-stream processing in regulating nutrient export, yet the influence of temporal variability in stream metabolism on net nutrient uptake has not been explicitly addressed. Streamwater DIN and SRP concentrations in Walker Branch, a first-order deciduous forest stream in eastern Tennessee, show a repeated pattern of annual maxima in summer and biannual minima in spring and autumn. Temporal variations in catchment hydrologic flowpaths result in lower winter and higher summer nutrient concentrations, but do not explain the spring and autumn nutrient minima. Ambient nutrient uptake rates were measured 2-3 times per weekmore » over an 18-mo period and compared to daily rates of gross primary production (GPP) and ecosystem respiration (ER) to examine the influence of in-stream biotic activity on nutrient export. GPP and ER rates explained 85% of the variation in net DIN retention with high net NO3- uptake (and lower net NH4+ release) rates occurring during spring and autumn and net DIN release in summer. Diel nutrient concentration patterns were examined several times throughout the year to determine the relative importance of autotrophic and heterotrophic activity on net nutrient uptake. High spring GPP corresponded to daily decreases in NO3- over the illuminated hours resulting in high diel NO3- amplitude which dampened as the canopy closed. GPP explained 91% of the variance in diel NO3- amplitude. In contrast, the autumn nutrient minima was largely explained by heterotrophic respiration since GPP remained low and little diel NO3- variation was observed during the autumn.« less
Fine-Scale Movements of the Broadnose Sevengill Shark and Its Main Prey, the Gummy Shark
Barnett, Adam; Abrantes, Kátya G.; Stevens, John D.; Bruce, Barry D.; Semmens, Jayson M.
2010-01-01
Information on the fine-scale movement of predators and their prey is important to interpret foraging behaviours and activity patterns. An understanding of these behaviours will help determine predator-prey relationships and their effects on community dynamics. For instance understanding a predator's movement behaviour may alter pre determined expectations of prey behaviour, as almost any aspect of the prey's decisions from foraging to mating can be influenced by the risk of predation. Acoustic telemetry was used to study the fine-scale movement patterns of the Broadnose Sevengill shark Notorynchus cepedianus and its main prey, the Gummy shark Mustelus antarcticus, in a coastal bay of southeast Tasmania. Notorynchus cepedianus displayed distinct diel differences in activity patterns. During the day they stayed close to the substrate (sea floor) and were frequently inactive. At night, however, their swimming behaviour continually oscillated through the water column from the substrate to near surface. In contrast, M. antarcticus remained close to the substrate for the entire diel cycle, and showed similar movement patterns for day and night. For both species, the possibility that movement is related to foraging behaviour is discussed. For M. antarcticus, movement may possibly be linked to a diet of predominantly slow benthic prey. On several occasions, N. cepedianus carried out a sequence of burst speed events (increased rates of movement) that could be related to chasing prey. All burst speed events during the day were across the substrate, while at night these occurred in the water column. Overall, diel differences in water column use, along with the presence of oscillatory behaviour and burst speed events suggest that N. cepedianus are nocturnal foragers, but may opportunistically attack prey they happen to encounter during the day. PMID:21151925
Diel cycles in dissolved metal concentrations in streams: Occurrence and possible causes
Nimick, David A.; Gammons, Christopher H.; Cleasby, Thomas E.; Madison, James P.; Skaar, Don; Brick, Christine M.
2003-01-01
Substantial diel (24‐hour) cycles in dissolved (0.1‐μm filtration) metal concentrations were observed during low flow for 18 sampling episodes at 14 sites on 12 neutral and alkaline streams draining historical mining areas in Montana and Idaho. At some sites, concentrations of Cd, Mn, Ni, and Zn increased as much as 119, 306, 167, and 500%, respectively, from afternoon minimum values to maximum values shortly after sunrise. Arsenic concentrations exhibited the inverse temporal pattern with increases of up to 54%. Variations in Cu concentrations were small and inconsistent. Diel metal cycles are widespread and persistent, occur over a wide range of metal concentrations, and likely are caused primarily by instream geochemical processes. Adsorption is the only process that can explain the inverse temporal patterns of As and the divalent metals. Diel metal cycles have important implications for many types of water‐quality studies and for understanding trace‐metal mobility.
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.
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.
Chadee, D D; Martinez, R
2000-12-01
The diel landing/biting periodicity of the Trinidad strain of Aedes aegypti (L.) was monitored using human-bait during January-August 1999. Hourly light intensities were measured both indoors and outdoors at both urban and rural sites. The periodicity of females was diurnal and nocturnal, with 90% arriving during daylight and twilight and 10% during the night. The pattern of landing was trimodal, with consistent peaks at 0700 h, 1100 h and 1700 h. The diel periodicities at indoor and outdoor urban sites were virtually identical. In contrast, the periodicities in rural areas differed, with no nocturnal activities being recorded at indoor and outdoor sites. At both urban and rural sites, larger numbers of adults were collected outside than inside houses. A significant correlation between light intensities and mosquito landing patterns was observed. The implications of the changing landing patterns of Ae. aegypti within urban areas are discussed in light of the epidemiology and control of dengue fever in Trinidad.
Diel Surface Temperature Range Scales with Lake Size
Woolway, R. Iestyn; Jones, Ian D.; Maberly, Stephen C.; French, Jon R.; Livingstone, David M.; Monteith, Donald T.; Simpson, Gavin L.; Thackeray, Stephen J.; Andersen, Mikkel R.; Battarbee, Richard W.; DeGasperi, Curtis L.; Evans, Christopher D.; de Eyto, Elvira; Feuchtmayr, Heidrun; Hamilton, David P.; Kernan, Martin; Krokowski, Jan; Rimmer, Alon; Rose, Kevin C.; Rusak, James A.; Ryves, David B.; Scott, Daniel R.; Shilland, Ewan M.; Smyth, Robyn L.; Staehr, Peter A.; Thomas, Rhian; Waldron, Susan; Weyhenmeyer, Gesa A.
2016-01-01
Ecological and biogeochemical processes in lakes are strongly dependent upon water temperature. Long-term surface warming of many lakes is unequivocal, but little is known about the comparative magnitude of temperature variation at diel timescales, due to a lack of appropriately resolved data. Here we quantify the pattern and magnitude of diel temperature variability of surface waters using high-frequency data from 100 lakes. We show that the near-surface diel temperature range can be substantial in summer relative to long-term change and, for lakes smaller than 3 km2, increases sharply and predictably with decreasing lake area. Most small lakes included in this study experience average summer diel ranges in their near-surface temperatures of between 4 and 7°C. Large diel temperature fluctuations in the majority of lakes undoubtedly influence their structure, function and role in biogeochemical cycles, but the full implications remain largely unexplored. PMID:27023200
Gorman, Owen T.; Yule, Daniel L.; Stockwell, Jason D.
2012-01-01
Diel migration patterns of fishes in nearshore (15–80 m depth) and offshore (>80 m) waters of Lake Superior were examined to assess the potential for diel migration to link benthic and pelagic, and nearshore and offshore habitats. In our companion article, we described three types of diel migration: diel vertical migration (DVM), diel bank migration (DBM), and no diel migration. DVM was expressed by fishes migrating from benthopelagic to pelagic positions and DBM was expressed by fishes migrating horizontally from deep to shallow waters at night. Fishes not exhibiting diel migration typically showed increased activity by moving from benthic to benthopelagic positions within demersal habitat. The distribution and biomass of fishes in Lake Superior was characterized by examining 704 bottom trawl samples collected between 2001 and 2008 from four depth zones: ≤40, 41–80, 81–160, and >160 m. Diel migration behaviors of fishes described in our companion article were applied to estimates of areal biomass (kg ha−1) for each species by depth zone. The relative strength of diel migrations were assessed by applying lake area to areal biomass estimates for each species by depth zone to yield estimates of lake-wide biomass (metric tonnes). Overall, species expressing DVM accounted for 83%, DBM 6%, and non-migration 11% of the total lake-wide community biomass. In nearshore waters, species expressing DVM represented 74% of the biomass, DBM 25%, and non-migration 1%. In offshore waters, species expressing DVM represented 85%, DBM 1%, and non-migration 14% of the biomass. Of species expressing DVM, 83% of total biomass occurred in offshore waters. Similarly, 97% of biomass of non-migrators occurred in offshore waters while 83% of biomass of species expressing DBM occurred in nearshore waters. A high correlation (R2 = 0.996) between lake area and community biomass by depth zone resulted in 81% of the lake-wide biomass occurring in offshore waters. Accentuating this nearshore-offshore trend was one of increasing estimated total areal biomass of the fish community with depth zone, which ranged from 13.71 kg ha−1 at depths ≤40 m to 18.81 kg ha−1 at depths >160 m, emphasizing the importance of the offshore fish community to the lake ecosystem. The prevalence of diel migration expressed by Lake Superior fishes increases the potential of fish to link benthic and pelagic and shallow and deepwater habitats. These linkages enhance the potential for habitat coupling, a condition where habitats become interconnected and interdependent through transfers of energy and nutrients. Habitat coupling facilitates energy and nutrient flow through a lake ecosystem, thereby increasing productivity, especially in large lakes where benthic and pelagic, and nearshore and offshore habitats are often well separated. We propose that the application of biomass estimates to patterns of diel migration in fishes can serve as a useful metric for assessing the potential for habitat linkages and habitat coupling in lake ecosystems, and provide an important indicator of ecosystem health and function. The decline of native Lake Trout and ciscoes and recent declines in exotic Alewife and Rainbow Smelt populations in other Great Lakes have likely reduced the capacity for benthic-pelagic coupling in these systems compared to Lake Superior. We recommend comparing the levels and temporal changes in diel migration in other Great Lakes as a means to assess changes in the relative health and function of these ecosystems.
K.R. Matthews
1996-01-01
Abstract.âI used radio transmitters to determine the diel habitat use and movement patterns of California golden trout Oncorhynchus mykiss aquabonita inside and outside cattle exclosures on the South Fork Kern River, Golden Trout Wilderness, California. Twenty-three golden trout were monitored from September 10 to 19, 1993, during 216 diel-tracking hours at four study...
Assessing diel variation of CH4 flux from rice paddies through temperature patterns
NASA Astrophysics Data System (ADS)
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.
Temple, Andrew J; Tregenza, Nick; Amir, Omar A; Jiddawi, Narriman; Berggren, Per
2016-01-01
Understanding temporal patterns in distribution, occurrence and behaviour is vital for the effective conservation of cetaceans. This study used cetacean click detectors (C-PODs) to investigate spatial and temporal variation in occurrence and foraging activity of the Indo-Pacific bottlenose (Tursiops aduncus) and Indian Ocean humpback (Sousa plumbea) dolphins resident in the Menai Bay Conservation Area (MBCA), Zanzibar, Tanzania. Occurrence was measured using detection positive minutes. Inter-click intervals were used to identify terminal buzz vocalisations, allowing for analysis of foraging activity. Data were analysed in relation to spatial (location) and temporal (monsoon season, diel phase and tidal phase) variables. Results showed significantly increased occurrence and foraging activity of dolphins in southern areas and during hours of darkness. Higher occurrence at night was not explained by diel variation in echolocation rate and so were considered representative of occurrence patterns. Both tidal phase and monsoon season influenced occurrence but results varied among sites, with no general patterns found. Foraging activity was greatest during hours of darkness, High water and Flood tidal phases. Comparisons of echolocation data among sites suggested differences in the broadband click spectra of MBCA dolphins, possibly indicative of species differences. These dolphin populations are threatened by unsustainable fisheries bycatch and tourism activities. The spatial and temporal patterns identified in this study have implications for future conservation and management actions with regards to these two threats. Further, the results indicate future potential for using passive acoustics to identify and monitor the occurrence of these two species in areas where they co-exist.
Diel changes in the near-surface biomass of zooplankton and the carbon content of vertical migrants
NASA Astrophysics Data System (ADS)
Hays, Graeme C.; Harris, Roger P.; Head, Robert N.
Zooplankton biomass and the carbon content of vertical migrants were measured in the NE Atlantic (36.5°N, 19.2°W) between 11 and 18 July 1996 as part of the Plankton Reactivity in the Marine Environment (PRIME) programme. The increase in zooplankton biomass near the surface (0-100 m) at night compared to during the day suggested that diel vertical migration was an important feature at this site. For three species of vertically migrant copepods, Pleuromamma pisekii, P. gracilis and P. abdominalis, the carbon content of individuals collected at dusk was significantly less than for individuals collected at dawn, with this reduction being 6.2, 7.3 and 14.8%, respectively. This dawn-dusk reduction in carbon content is consistent with the diel pattern of feeding and fasting exhibited by vertical migrants and supports the suggestion that migrating zooplankton will cause an active export of carbon from the surface layers.
NASA Astrophysics Data System (ADS)
von Haden, A.; Marin-Spiotta, E.; Jackson, R. D.; Kucharik, C. J.
2016-12-01
A high proportion of carbon lost from terrestrial ecosystems occurs via soil CO2 respiration. Soil respiration is comprised of two contrasting sources: heterotrophic respiration (RH) from the decomposition of organic matter and autotrophic respiration (RA) from plant root metabolism. Since the two sources of soil respiration vary widely in their origin, the controls of each source are also likely to differ. However, the challenge of partitioning soil respiration sources in situ has limited our mechanistic understanding of RH and RA. Our objective was to evaluate the in situ diurnal controls of RH and RA in maize (Zea mays L.) and switchgrass (Panicum virgatum L.) bioenergy cropping systems. We hypothesized that both RH and RA would follow diurnal soil temperature trends, but that RA would also respond to diel patterns of photosynthetically active radiation (PAR). We also expected that diurnal soil respiration patterns would vary significantly within the growing season. We evaluated our hypothesis with six diurnal soil respiration campaigns during the 2015 and 2016 growing seasons at Arlington, WI, USA. RH showed clear oscillating diel trends, typically peaking in the mid-afternoon when near-surface soil temperatures were highest. Diurnal RA patterns were more nuanced than RH, but were generally highest in the late afternoon and showed the most pronounced diel trends during peak growing season in July. RA also tended to spike in concert with PAR, but this effect was much more prominent in maize than switchgrass. Continuing efforts will attempt to quantitatively separate the effects of soil temperature and PAR on RA.
Taybi, Tahar; Cushman, John C; Borland, Anne M
2017-11-01
Nocturnal degradation of transitory starch is a limiting factor for the optimal function of crassulacean acid metabolism and must be coordinated with phosphoenolypyruvate carboxylase (PEPC)-mediated CO 2 uptake to optimise carbon gain over the diel cycle. The aim of this study was to test the hypothesis that nocturnal carboxylation is coordinated with starch degradation in CAM via a mechanism whereby the products of these pathways regulate diel transcript abundance and enzyme activities for both processes. To test this hypothesis, a starch and CAM-deficient mutant of Mesembryanthemum crystallinum was compared with wild type plants under well-watered and saline (CAM-inducing) conditions. Exposure to salinity increased the transcript abundance of genes required for nocturnal carboxylation, starch and sucrose degradation in both wild type and mutant, but the transcript abundance of several of these genes was not sustained over the dark period in the low-carbohydrate, CAM-deficient mutant. The diel pattern of transcript abundance for PEPC mirrored that of PEPC protein, as did the transcripts, protein, and activity of chloroplastic starch phosphorylase in both wild type and mutant, suggesting robust diel coordination of these metabolic processes. Activities of several amylase isoforms were low or lacking in the mutant, whilst the activity of a cytosolic isoform of starch phosphorylase was significantly elevated, indicating contrasting modes of metabolic regulation for the hydrolytic and phosphorylytic routes of starch degradation. Externally supplied sucrose resulted in an increase in nocturnal transcript abundance of genes required for nocturnal carboxylation and starch degradation. These results demonstrate that carbohydrates impact on transcriptional and post-transcriptional regulation of nocturnal carboxylation and starch degradation in CAM. Copyright © 2017 Elsevier GmbH. All rights reserved.
Gary, R E; Foster, W A
2006-09-01
Little is known about the sugar-feeding behaviour of equatorial Africa's principal vector of malaria, Anopheles gambiae Giles (Diptera: Culicidae). It is suspected to feed on plant sugar infrequently, but possibly the timing depends on environmental circumstances, and males may differ markedly from females. These points of uncertainty were clarified in the laboratory, by monitoring both diel and longterm sugar-feeding activity in both sexes. Males fed on sugar in a nocturnal diel rhythm closely approximating non-specific flight activity. Female diel sugar-feeding patterns resembled published rhythms and cycles of host seeking. Males sugar fed nightly at an average frequency of about twice per night, sustained over 17 days. This was substantially higher than the sugar-feeding frequency of females that were allowed both blood and oviposition sites every night: they averaged about one sugar feed in every 4 nights. These females fed on sugar between gonotrophic cycles, after eggs were mature but before the next bloodmeal. They did not sugar feed during the 2 days after blood feeding, while blood was being digested and the eggs developed. A slight delay in the availability of either the oviposition site or blood led to an increase in female sugar-feeding frequency: they averaged more than once per night until the delayed resource was made available. These observations support the conclusion that sugar feeding is a normal part of the biology of both sexes of An. gambiae.
Leroy, Emmanuelle C; Samaran, Flore; Bonnel, Julien; Royer, Jean-Yves
2016-01-01
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.
Leroy, Emmanuelle C.; Samaran, Flore; Bonnel, Julien; Royer, Jean-Yves
2016-01-01
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. PMID:27828976
DIEL FLUX OF DISSOLVED CARBOHYDRATE IN A SALT MARSH AND A SIMULATED ESTUARINE ECOSYSTEM
The concentrations of total dissolved carbohydrate (TCHO), monosaccharide (MCHO) and polysaccharide (PCHO) were followed over a total of ten diel cycles in a salt marsh and a 13 cu m seawater tank simulating an estuarine ecosystem. Their patterns are compared to those for total d...
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.
Dong, Suwei; Cahill, Katharine J; Kang, Moon-Il; Colburn, Nancy H; Henrich, Curtis J; Wilson, Jennifer A; Beutler, John A; Johnson, Richard P; Porco, John A
2011-11-04
We have accomplished a parallel screen of cycloaddition partners for o-quinols utilizing a plate-based microwave system. Microwave irradiation improves the efficiency of retro-Diels-Alder/Diels-Alder cascades of o-quinol dimers which generally proceed in a diastereoselective fashion. Computational studies indicate that asynchronous transition states are favored in Diels-Alder cycloadditions of o-quinols. Subsequent biological evaluation of a collection of cycloadducts has identified an inhibitor of activator protein-1 (AP-1), an oncogenic transcription factor.
Acoustic and temporal partitioning of cicada assemblages in city and mountain environments.
Shieh, Bao-Sen; Liang, Shih-Hsiung; Chiu, Yuh-Wen
2015-01-01
Comparing adaptations to noisy city environments with those to natural mountain environments on the community level can provide significant insights that allow an understanding of the impact of anthropogenic noise on invertebrates that employ loud calling songs for mate attraction, especially when each species has its distinct song, as in the case of cicadas. In this study, we investigated the partitioning strategy of cicada assemblages in city and mountain environments by comparing the acoustic features and calling activity patterns of each species, recorded using automated digital recording systems. Our comparison of activity patterns of seasonal and diel calling revealed that there was no significant temporal partitioning of cicada assemblages in either environment. In addition, there was no correlation between the acoustic distance based on spectral features and temporal segregation. Heterospecific spectral overlap was low in both city and mountain environments, although city and mountain cicada assemblages were subject to significantly different levels of anthropogenic or interspecific noise. Furthermore, for the common species found in both environments, the calling activity patterns at both seasonal and diel time scales were significantly consistent across sites and across environments. We suggest that the temporal calling activity is constrained by endogenous factors for each species and is less flexible in response to external factors, such as anthropogenic noise. As a result, cicada assemblages in city environments with low species diversity do not demonstrate a more significant temporal partitioning than those in mountain environments with high species diversity.
Acoustic and Temporal Partitioning of Cicada Assemblages in City and Mountain Environments
Shieh, Bao-Sen; Liang, Shih-Hsiung; Chiu, Yuh-Wen
2015-01-01
Comparing adaptations to noisy city environments with those to natural mountain environments on the community level can provide significant insights that allow an understanding of the impact of anthropogenic noise on invertebrates that employ loud calling songs for mate attraction, especially when each species has its distinct song, as in the case of cicadas. In this study, we investigated the partitioning strategy of cicada assemblages in city and mountain environments by comparing the acoustic features and calling activity patterns of each species, recorded using automated digital recording systems. Our comparison of activity patterns of seasonal and diel calling revealed that there was no significant temporal partitioning of cicada assemblages in either environment. In addition, there was no correlation between the acoustic distance based on spectral features and temporal segregation. Heterospecific spectral overlap was low in both city and mountain environments, although city and mountain cicada assemblages were subject to significantly different levels of anthropogenic or interspecific noise. Furthermore, for the common species found in both environments, the calling activity patterns at both seasonal and diel time scales were significantly consistent across sites and across environments. We suggest that the temporal calling activity is constrained by endogenous factors for each species and is less flexible in response to external factors, such as anthropogenic noise. As a result, cicada assemblages in city environments with low species diversity do not demonstrate a more significant temporal partitioning than those in mountain environments with high species diversity. PMID:25590620
Wu, Shuang; Chen, Jie; Li, Chen; Kong, Delei; Yu, Kai; Liu, Shuwei; Zou, Jianwen
2018-02-07
Agricultural nitrate leaching and runoff incurs high nitrogen loads in agricultural irrigation watersheds, constituting one of important sources of atmospheric nitrous oxide (N 2 O). Two independent sampling campaigns of N 2 O flux measurement over diel cycles and N 2 O flux measurements once a week over annual cycles were carried out in an agricultural irrigation watershed in southeast China using floating chamber (chamber-based) and gas transfer equation (model-based) methods. The diel and seasonal patterns of N 2 O fluxes did not differ between the two measurement methods. The diel variation in N 2 O fluxes was characterized by the pattern that N 2 O fluxes were greater during nighttime than daytime periods with a single flux peak at midnight. The diel variation in N 2 O fluxes was closely associated with water environment and chemistry. The time interval of 9:00-11:00 a.m. was identified to be the sampling time best representing daily N 2 O flux measurements in agricultural irrigation watersheds. Seasonal N 2 O fluxes showed large variation, with some flux peaks corresponding to agricultural irrigation and drainage episodes and heavy rainfall during the crop-growing period of May to November. On average, N 2 O fluxes calculated by model-based methods were 27% lower than those determined by the chamber-based techniques over diel or annual cycles. Overall, more measurement campaigns are highly needed to assess regional agricultural N 2 O budget with low uncertainties.
Genetic Selection for Improved Abzymes in E. Coli
1994-08-03
immunoassay to scemen antibody phage libraries directly for catalysis of a bimolecular Diels - Alder reaction and have identified several active clones...sensitive growth selection assay in F coli for catalysts with chorismate mutase activity; and (3) we identified new abzymes for a Diels - Alder ...generated combinatorial antibody libraries from mRNA isolated from the spleens of mice hyperimmunized with transition state analogs for Diels - Alder and
Dong, Suwei; Cahill, Kath arine J.; Kang, Moon -Il; Colburn, Nancy H.; Henrich, Curtis J.; Wilson, Jennifer A.; Beutler, John A.; Johnson, Richard P.; Porco, John A.
2011-01-01
We have accomplished a parallel screen of cycloaddition partners for ortho-quinols utilizing a plate-based microwave system. Microwave irradiation improves the efficiency of retro-Diels-Alder/Diels-Alder cascades of ortho-quinol dimers which generally proceed in a diastereoselective fashion. Computational studies indicate that asynchronous transition states are favored in Diels-Alder cycloadditions of ortho-quinols. Subsequent biological evaluation of a collection of cycloadducts has identified an inhibitor of activator protein-1 (AP-1), an oncogenic transcription factor. PMID:21942286
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.
NASA Astrophysics Data System (ADS)
Isla, Alejandro; Scharek, Renate; Latasa, Mikel
2015-03-01
The diel vertical migration (DVM) of zooplankton contributes to the biological pump transporting material from surface to deep waters. We examined the DVM of the zooplankton community in different size fractions (53-200 μm, 200-500 μm, 500-1000 μm, 1000-2000 μm and > 2000 μm) during three cruises carried out in the open NW Mediterranean Sea. We assessed their metabolic rates from empirical published relationships and estimated the active fluxes of dissolved carbon to the mesopelagic zone driven by migrant zooplankton. Within the predominantly oligotrophic Mediterranean Sea, the NW region is one of the most productive ones, with a seasonal cycle characterized by a prominent spring bloom. The study area was visited at three different phases of the seasonal cycle: during the spring bloom, the post-bloom, and strongly stratified oligotrophic conditions. We found seasonal differences in DVM, less evident during the bloom. Changes in DVM intensity were related to the composition of the zooplanktonic assemblage, which also varied between cruises. Euphausiids appeared as the most active migrants in all seasons, and their life cycle conditioned the observed pattern. Immature stages, which are unable to perform large diel vertical movements, dominated during the bloom, in contrast to the higher relative importance of migrating adults in the other two sampling periods. The amount of dissolved carbon exported was determined by the migrant zooplankton biomass, being highest during the post-bloom (2.2 mmol C respired m- 2 d- 1, and up to 3.1 mmol C exported m- 2 d- 1 when DOC release estimations are added). The active transport by diel migrants represented a substantial contribution to total carbon export to deep waters, especially under stratified oligotrophic conditions, revealing the importance of zooplankton in the biological pump operating in the study area.
Vocal activity of lesser galagos (Galago spp.) at zoos.
Schneiderová, Irena; Zouhar, Jan; Štefanská, Lucie; Bolfíková, Barbora Černá; Lhota, Stanislav; Brandl, Pavel
2016-01-01
Almost nothing is known about the natural vocal behavior of lesser galagos living in zoos. This is perhaps because they are usually kept in nocturnal exhibits separated from the visitors by a transparent and acoustically insulating glass barrier. The aim of the present study was therefore to fill this gap in knowledge of the vocal behavior of lesser galagos from zoos. This knowledge might be beneficial because the vocalizations of these small primates can be used for species determination. We performed a 10-day-long acoustic monitoring of vocal activity in each of seven various groups of Galago senegalensis and G. moholi living at four zoos. We quantitatively evaluated the occurrence of four loud vocalization types present in both species, including the most species-specific advertisement call. We found that qualitative as well as quantitative differences exist in the vocal behavior of the studied groups. We confirmed that the observed vocalization types can be collected from lesser galagos living at zoos, and the success can be increased by selecting larger and more diverse groups. We found two distinct patterns of diel vocal activity in the most vocally active groups. G. senegalensis groups were most vocally active at the beginning and at the end of their activity period, whereas one G. moholi group showed an opposite pattern. The latter is surprising, as it is generally accepted that lesser galagos emit advertisement calls especially at dawn and dusk, i.e., at the beginning and at the end of their diel activity. © 2016 Wiley Periodicals, Inc.
NASA Astrophysics Data System (ADS)
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 extreme events (i.e. major decrease in rainfall) and (2) the large-scale influence that these extreme events can exert on recruitment processes in tropical estuarine fish assemblages.
Foster, S P
2000-03-01
Pheromone titer in moths is a product of three processes occurring in or at the surface of the pheromone gland: biosynthesis, release, and intraglandular degradation, of pheromone. Changes in titers of sex pheromone, the fatty acyl pheromone analog (FAPA), and tetradecanoate, a pheromone biosynthetic intermediate, were studied in detail in the lightbrown apple moth, Epiphyas postvittana (Walker). Although changes in the pheromone titers in a day were relatively small, with the peak titer being 2-3 times greater than that at the trough, pheromone titer did show a distinct diel periodicity. Titer of the FAPA showed a similar, but less variable, diel pattern, but tetradecanoate titer showed little or no diel pattern. The pattern of pheromone titer suggested that females biosynthesize pheromone at two different rates during the photoperiod: a high rate during the latter half of the photophase and most of the scotophase, which is associated with a high pheromone titer, and a low rate throughout the first half of the photophase, which is associated with a low titer. Consistent with data on commencement of copulation, pheromone was released from the second hour of the scotophase through to the eighth hour. Pheromone release rate during this period appeared to be similar to the rate of pheromone biosynthesis. In contrast to the other two processes, pheromone degradation did not appear to have a diel pattern. Females decapitated at different times of the photoperiod showed a similar decline in pheromone titer, consistent with the reaction kinetics being first order in pheromone titer.
Bogdan, Vlastimil; Jůnek, Tomáš; Jůnková Vymyslická, Pavla
2016-01-01
The vertebrate fauna of the Philippines, known for its diversity and high proportion of endemic species, comprises mainly small- to medium-sized forms with a few large exceptions. As with other tropical ecosystems, the major threats to wildlife are habitat loss, hunting and invasive species, of which the feral cat (Felis catus) is considered the most damaging. Our camera-trapping study focused on a terrestrial vertebrate species inventory on Bohol Island and tempo-spatial co-occurrences of feral cats with their prey and competitors. The survey took place in the Rajah Sikatuna Protected Landscape, and we examined the primary rainforest, its border with agricultural land, and rural areas in the vicinity of villages. Altogether, over 2,885 trap days we captured 30 species of vertebrates-10 mammals (including Sus philippensis), 19 birds and one reptile, Varanus cumingi. We trapped 81.8% of expected vertebrates. Based on the number of events, the most frequent native species was the barred rail (Gallirallus torquatus). The highest overlap in diel activity between cats and potential prey was recorded with rodents in rural areas (Δ = 0.62); the lowest was in the same habitat with ground-dwelling birds (Δ = 0.40). Cat activity was not recorded inside the rainforest; in other habitats their diel activity pattern differed. The cats' activity declined in daylight in the proximity of humans, while it peaked at the transition zone between rainforest and fields. Both rodents and ground-dwelling birds exhibited a shift in activity levels between sites where cats were present or absent. Rodents tend to become active by day in cat-free habitats. No cats' temporal response to co-occurrences of civets (Paradoxurus hermaphroditus and Viverra tangalunga) was found but cats in diel activity avoided domestic dogs (Canis lupus familiaris). Our first insight into the ecology of this invasive predator in the Philippines revealed an avoidance of homogeneous primary rainforest and a tendency to forage close to human settlements in heterogeneous habitats. A detailed further investigation of the composition of the cat's diet, as well as ranging pattern, is still needed.
Bogdan, Vlastimil; Jůnková Vymyslická, Pavla
2016-01-01
The vertebrate fauna of the Philippines, known for its diversity and high proportion of endemic species, comprises mainly small- to medium-sized forms with a few large exceptions. As with other tropical ecosystems, the major threats to wildlife are habitat loss, hunting and invasive species, of which the feral cat (Felis catus) is considered the most damaging. Our camera-trapping study focused on a terrestrial vertebrate species inventory on Bohol Island and tempo-spatial co-occurrences of feral cats with their prey and competitors. The survey took place in the Rajah Sikatuna Protected Landscape, and we examined the primary rainforest, its border with agricultural land, and rural areas in the vicinity of villages. Altogether, over 2,885 trap days we captured 30 species of vertebrates–10 mammals (including Sus philippensis), 19 birds and one reptile, Varanus cumingi. We trapped 81.8% of expected vertebrates. Based on the number of events, the most frequent native species was the barred rail (Gallirallus torquatus). The highest overlap in diel activity between cats and potential prey was recorded with rodents in rural areas (Δ = 0.62); the lowest was in the same habitat with ground-dwelling birds (Δ = 0.40). Cat activity was not recorded inside the rainforest; in other habitats their diel activity pattern differed. The cats’ activity declined in daylight in the proximity of humans, while it peaked at the transition zone between rainforest and fields. Both rodents and ground-dwelling birds exhibited a shift in activity levels between sites where cats were present or absent. Rodents tend to become active by day in cat-free habitats. No cats’ temporal response to co-occurrences of civets (Paradoxurus hermaphroditus and Viverra tangalunga) was found but cats in diel activity avoided domestic dogs (Canis lupus familiaris). Our first insight into the ecology of this invasive predator in the Philippines revealed an avoidance of homogeneous primary rainforest and a tendency to forage close to human settlements in heterogeneous habitats. A detailed further investigation of the composition of the cat’s diet, as well as ranging pattern, is still needed. PMID:27602271
Landscape-level variation in disease susceptibility related to shallow-water hypoxia.
Breitburg, Denise L; Hondorp, Darryl; Audemard, Corinne; Carnegie, Ryan B; Burrell, Rebecca B; Trice, Mark; Clark, Virginia
2015-01-01
Diel-cycling hypoxia is widespread in shallow portions of estuaries and lagoons, especially in systems with high nutrient loads resulting from human activities. Far less is known about the effects of this form of hypoxia than deeper-water seasonal or persistent low dissolved oxygen. We examined field patterns of diel-cycling hypoxia and used field and laboratory experiments to test its effects on acquisition and progression of Perkinsus marinus infections in the eastern oyster, Crassostrea virginica, as well as on oyster growth and filtration. P. marinus infections cause the disease known as Dermo, have been responsible for declines in oyster populations, and have limited success of oyster restoration efforts. The severity of diel-cycling hypoxia varied among shallow monitored sites in Chesapeake Bay, and average daily minimum dissolved oxygen was positively correlated with average daily minimum pH. In both field and laboratory experiments, diel-cycling hypoxia increased acquisition and progression of infections, with stronger results found for younger (1-year-old) than older (2-3-year-old) oysters, and more pronounced effects on both infections and growth found in the field than in the laboratory. Filtration by oysters was reduced during brief periods of exposure to severe hypoxia. This should have reduced exposure to waterborne P. marinus, and contributed to the negative relationship found between hypoxia frequency and oyster growth. Negative effects of hypoxia on the host immune response is, therefore, the likely mechanism leading to elevated infections in oysters exposed to hypoxia relative to control treatments. Because there is considerable spatial variation in the frequency and severity of hypoxia, diel-cycling hypoxia may contribute to landscape-level spatial variation in disease dynamics within and among estuarine systems.
Diel fluctuations of viscosity-driven riparian inflow affect streamflow DOC concentration
NASA Astrophysics Data System (ADS)
Schwab, Michael P.; Klaus, Julian; Pfister, Laurent; Weiler, Markus
2018-04-01
Diel fluctuations of stream water DOC concentrations are generally explained by a complex interplay of different instream processes. We measured the light absorption spectrum of water and DOC concentrations in situ and with high frequency by means of a UV-Vis spectrometer during 18 months at the outlet of a forested headwater catchment in Luxembourg (0.45 km2). We generally observed diel DOC fluctuations with a maximum in the afternoon during days that were not affected by rainfall-runoff events. We identified an increased inflow of terrestrial DOC to the stream in the afternoon, causing the DOC maxima in the stream. The terrestrial origin of the DOC was derived from the SUVA-254 (specific UV absorbance at 254 nm) index, which is a good indicator for the aromaticity of DOC. In the studied catchment, the most likely process that can explain the diel DOC input variations towards the stream is the so-called viscosity effect. The water temperature in the upper parts of the saturated riparian zone is increasing during the day, leading to a lower viscosity and therefore a higher hydraulic conductivity. Consequently, more water from areas that are rich in terrestrial DOC passes through the saturated riparian zone and contributes to streamflow in the afternoon. We believe that not only diel instream processes, but also viscosity-driven diel fluctuations of terrestrial DOC input should be considered to explain diel DOC patterns in streams.
NASA Astrophysics Data System (ADS)
Colombini, Isabella; Fallaci, Mario; Gagnarli, Elena; Rossano, Claudia; Scapini, Felicita; Chelazzi, Lorenzo
2013-01-01
The behavioural ecology of a sub-population of Talitrus saltator living on the sandy shore of the Maremma Regional Park (Italy) was compared with that of Orchestia gammarellus inhabiting the retrodunal dune slack area. Monthly monitoring over a year determined the mean distribution patterns, their changes and whether these overlapped. Standard pitfall traps were placed along transects across the beach-dune-dune slack area. Experiments analysed the diel activity rhythms during spring and the activity patterns of the different age classes and the two sexes were compared within and between species. Local environmental conditions were registered with a microclimatic station. During May and September, plant hummocks were monitored to see whether surface movements of O. gammarellus could be restricted to certain periods of the year and to estimate densities within the vegetation. The plant biomass and moisture conditions within the hummocks were also recorded and substratum samples were collected at the base of the shrubs for laboratory analysis. To test for visual cues, orientation experiments with and without landscape view were carried out on the beach during morning and afternoon hours and contemporaneously for each species. Experiments to test the diel variation of scototaxis to a black shape were also performed over a 24 h period of time under controlled conditions. There was a spatial partitioning of the two species, with T. saltator moving along a sea-land axis according to diel and seasonal changes and with some individuals reaching the back of the dune in particular environmental conditions. No spatial overlap with the zonation patterns of O. gammarellus was observed, which was restricted to the dune slack area. Nocturnal surface activity was observed for both species with juveniles peaking at dawn and with O. gammarellus being strictly more nocturnal than T. saltator. Orientation experiments showed a higher ability of T. saltator to orient towards the shoreline using solar and local cues, whereas O. gammarellus seemed to have a stronger scototaxis. Differences in the behavioural responses are discussed in terms of the species ecological adaptations to their particular habitats.
Oswald, Julie N; Norris, Thomas F; Yack, Tina M; Ferguson, Elizabeth L; Kumar, Anurag; Nissen, Jene; Bell, Joel
2016-01-01
Passive acoustic data collected from marine autonomous recording units deployed off Jacksonville, FL (from 13 September to 8 October 2009 and 3 December 2009 to 8 January 2010), were analyzed for detection of cetaceans and Navy sonar. Cetaceans detected included Balaenoptera acutorostrata, Eubalaena glacialis, B. borealis, Physeter macrocephalus, blackfish, and delphinids. E. glacialis were detected at shallow and, somewhat unexpectedly, deep sites. P. macrocephalus were characterized by a strong diel pattern. B. acutorostrata showed the strongest relationship between sonar activity and vocal behavior. These results provide a preliminary assessment of cetacean occurrence off Jacksonville and new insights on vocal responses to sonar.
ERIC Educational Resources Information Center
Shaw, Roosevelt; Severin, Ashika; Balfour, Miguel; Nettles, Columbus
2005-01-01
Two Diels-Alder reactions are described that are suitable for a MORE (microwave-induced organic reaction enhanced) experiment in the organic chemistry laboratory course. A second experiment in which the splitting patterns of the vinyl protons in the nuclear magnetic resonance (NMR) spectra of two MORE adducts are used in conjunction with molecular…
Doya, Carolina; Thomsen, Laurenz; Purser, Autun; Aguzzi, Jacopo
2016-01-01
Three benthic megafaunal species (i.e. sablefish Anoplopoma fimbria; pacific hagfish Eptatretus stoutii and a group of juvenile crabs) were tested for diel behavioral patterns at the methane hydrates site of Barkley Canyon (890 m depth), off Vancouver Island (BC, Canada). Fluctuations of animal counts in linear video-transects conducted with the Internet Operated Deep-Sea Crawler “Wally” in June, July and December of 2013, were used as proxy of population activity rhythms. Count time series and environmental parameters were analyzed under the hypothesis that the environmental conditioning of activity rhythms depends on the life habits of particular species (i.e. movement type and trophic level). Non-linear least squares modeling of biological time series revealed significant diel periods for sablefish in summer and for hagfish and crabs in December. Combined cross-correlation and redundancy (RDA) analyses showed strong relationships among environmental fluctuations and detected megafauna. In particular, sablefish presence during summer months was related to flow magnitude, while the activity of pacific hagfish and juvenile crabs in December correlated with change in chemical parameters (i.e. chlorophyll and oxygen concentrations, respectively). Waveform analyses of animal counts and environmental variables confirmed the phase delay during the 24 h cycle. The timing of detection of sablefish occurred under low flow velocities, a possible behavioral adaptation to the general hypoxic conditions. The proposed effect of chlorophyll concentrations on hagfish counts highlights the potential role of phytodetritus as an alternative food source for this opportunistic feeder. The juvenile crabs seemed to display a cryptic behavior, possibly to avoid predation, though this was suppressed when oxygen levels were at a minimum. Our results highlight the potential advantages such mobile observation platforms offer in multiparametric deep-sea monitoring in terms of both spatial and temporal resolution and add to the vastly understudied field of diel rhythms of deep-sea megafauna. PMID:27732626
Chatzievangelou, Damianos; Doya, Carolina; Thomsen, Laurenz; Purser, Autun; Aguzzi, Jacopo
2016-01-01
Three benthic megafaunal species (i.e. sablefish Anoplopoma fimbria; pacific hagfish Eptatretus stoutii and a group of juvenile crabs) were tested for diel behavioral patterns at the methane hydrates site of Barkley Canyon (890 m depth), off Vancouver Island (BC, Canada). Fluctuations of animal counts in linear video-transects conducted with the Internet Operated Deep-Sea Crawler "Wally" in June, July and December of 2013, were used as proxy of population activity rhythms. Count time series and environmental parameters were analyzed under the hypothesis that the environmental conditioning of activity rhythms depends on the life habits of particular species (i.e. movement type and trophic level). Non-linear least squares modeling of biological time series revealed significant diel periods for sablefish in summer and for hagfish and crabs in December. Combined cross-correlation and redundancy (RDA) analyses showed strong relationships among environmental fluctuations and detected megafauna. In particular, sablefish presence during summer months was related to flow magnitude, while the activity of pacific hagfish and juvenile crabs in December correlated with change in chemical parameters (i.e. chlorophyll and oxygen concentrations, respectively). Waveform analyses of animal counts and environmental variables confirmed the phase delay during the 24 h cycle. The timing of detection of sablefish occurred under low flow velocities, a possible behavioral adaptation to the general hypoxic conditions. The proposed effect of chlorophyll concentrations on hagfish counts highlights the potential role of phytodetritus as an alternative food source for this opportunistic feeder. The juvenile crabs seemed to display a cryptic behavior, possibly to avoid predation, though this was suppressed when oxygen levels were at a minimum. Our results highlight the potential advantages such mobile observation platforms offer in multiparametric deep-sea monitoring in terms of both spatial and temporal resolution and add to the vastly understudied field of diel rhythms of deep-sea megafauna.
Zhu, Jun; Hiltz, Jonathan; Tefashe, Ushula M; Mauzeroll, Janine; Lennox, R Bruce
2018-06-21
The chemical modification of an sp 2 hybridized carbon surface in a controllable manner is very challenging but also crucial for many applications. An inverse electron demand Diels-Alder (IEDDA) reaction using microcontact printing technique is introduced to spatially control the modification of a highly ordered pyrolytic graphite (HOPG) surface under ambient conditions. The covalent modification was characterized by Raman spectroscopy, XPS, and SECM. Tetrazine derivatives can effectively react with an HOPG surface and with microcontact printing methods resulting in spatially patterned surfaces being produced with micrometer-scale resolution. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Cove, Michael V.; Gardner, Beth; Simons, Theodore R.; Kays, Roland; O'Connell, Allan F.
2017-01-01
Feral and free-ranging domestic cats (Felis catus) can have strong negative effects on small mammals and birds, particularly in island ecosystems. We deployed camera traps to study free-ranging cats in national wildlife refuges and state parks on Big Pine Key and Key Largo in the Florida Keys, USA, and used spatial capture–recapture models to estimate cat abundance, movement, and activities. We also used stable isotope analyses to examine the diet of cats captured on public lands. Top population models separated cats based on differences in movement and detection with three and two latent groups on Big Pine Key and Key Largo, respectively. We hypothesize that these latent groups represent feral, semi-feral, and indoor/outdoor house cats based on the estimated movement parameters of each group. Estimated cat densities and activity varied between the two islands, with relatively high densities (~4 cats/km2) exhibiting crepuscular diel patterns on Big Pine Key and lower densities (~1 cat/km2) exhibiting nocturnal diel patterns on Key Largo. These differences are most likely related to the higher proportion of house cats on Big Pine relative to Key Largo. Carbon and nitrogen isotope ratios from hair samples of free-ranging cats (n = 43) provided estimates of the proportion of wild and anthropogenic foods in cat diets. At the population level, cats on both islands consumed mostly anthropogenic foods (>80% of the diet), but eight individuals were effective predators of wildlife (>50% of the diet). We provide evidence that cat groups within a population move different distances, exhibit different activity patterns, and that individuals consume wildlife at different rates, which all have implications for managing this invasive predator.
Diel Variation in Beaked Whale Diving Behavior
2008-01-01
While our results are only from a single study area and our sample size is small, diving patterns of these two species appear very stereotypic ...sharks of the genus Isistius (McSweeney et al. 2007). Cookie-cutter sharks are thought to exhibit diel vertical migrations, spending time near the...Mar. Mamm. Sci. 23: 666-687. 17 Mead, J.G. 1989. Beaked whales of the genus Mesoplodon. Pages 349-430 In S.H. Ridgway and R. Harrison
Movement, home range, and site fidelity of bluegills in a Great Plains Lake
Paukert, C.P.; Willis, D.W.; Bouchard, M.A.
2004-01-01
Little is known about the distribution, movement, and home ranges of bluegills Lepomis macrochirus in lentic environments. Therefore, the objectives of this study were to evaluate the seasonal and diel differences in movement rates, site fidelity, and home range of bluegills in a shallow, natural Great Plains lake. A total of 78 bluegills (200-273 mm total length) were implanted with radio transmitters in March and May 2000. Of these fish, 10 males and 10 females were randomly selected and located every 2 h during one 24-h period each month from April to September 2000. Bluegill movement peaked during midsummer: however, there was little difference in diel movements, suggesting relatively consistent movement throughout the 24-h period. Home range estimates (which included the 24-h tracking plus an additional six locations from the same fish located once per day for six consecutive days each month) ranged up to 172 ha, probably because only about half of the bluegills exhibited site fidelity during any month sampled. Bluegill movement did not appear to be strongly linked with water temperature, barometric pressure, or wind speed. These results suggest that bluegills move considerable distances and that many roam throughout this 332-ha shallow lake. However, diel patterns were not evident. Sampling bluegills in Great Plains lakes using passive gears (e.g., trap nets) may be most effective during the summer months, when fish are most active. Active sampling (e.g., electrofishing) may be more effective than the use of passive gears in spring and fall, when bluegills are less active.
Diel predator activity drives a dynamic landscape of fear
Kohl, Michel T.; Stahler, Daniel R.; Metz, Matthew C.; Forester, James D.; Kauffman, Matthew J.; Varley, Nathan; White, P.J.; Smith, Douglas W.; MacNulty, Daniel R.
2017-01-01
A "landscape of fear" (LOF) is a map that describes continuous spatial variation in an animal's perception of predation risk. The relief on this map reflects, for example, places that an animal avoids to minimize risk. Although the LOF concept is a potential unifying theme in ecology that is often invoked to explain the ecological and conservation significance of fear, quantified examples of a LOF over large spatial scales are lacking as is knowledge about the daily dynamics of a LOF. Despite theory and data to the contrary, investigators often assume, implicitly or explicitly, that a LOF is a static consequence of a predator's mere presence. We tested the prediction that a LOF in a large-scale, free-living system is a highly-dynamic map with "peaks" and "valleys" that alternate across the diel (24-hour) cycle in response to daily lulls in predator activity. We did so with extensive data from the case study of Yellowstone elk (Cervus elaphus) and wolves (Canis lupus) that was the original basis for the LOF concept. We quantified the elk LOF, defined here as spatial allocation of time away from risky places and times, across nearly 1000-km2 of northern Yellowstone National Park and found that it fluctuated with the crepuscular activity pattern of wolves, enabling elk to use risky places during wolf downtimes. This may help explain evidence that wolf predation risk has no effect on elk stress levels, body condition, pregnancy, or herbivory. The ability of free-living animals to adaptively allocate habitat use across periods of high and low predator activity within the diel cycle is an underappreciated aspect of animal behavior that helps explain why strong antipredator responses may trigger weak ecological effects, and why a LOF may have less conceptual and practical importance than direct killing.
The oxygen-18 isotope approach for measuring aquatic metabolism in high-productivity waters
Tobias, C.R.; Böhlke, J.K.; Harvey, J.W.
2007-01-01
We examined the utility of ??18O2 measurements in estimating gross primary production (P), community respiration (R), and net metabolism (P:R) through diel cycles in a productive agricultural stream located in the midwestern U.S.A. Large diel swings in O2 (??200 ??mol L-1) were accompanied by large diel variation in ??18O2 (??10???). Simultaneous gas transfer measurements and laboratory-derived isotopic fractionation factors for O2 during respiration (??r) were used in conjunction with the diel monitoring of O2 and ??18O2 to calculate P, R, and P:R using three independent isotope-based methods. These estimates were compared to each other and against the traditional "open-channel diel O2-change" technique that lacked ??18O2. A principal advantage of the ??18O2 measurements was quantification of diel variation in R, which increased by up to 30% during the day, and the diel pattern in R was variable and not necessarily predictable from assumed temperature effects on R. The P, R, and P:R estimates calculated using the isotope-based approaches showed high sensitivity to the assumed system fractionation factor (??r). The optimum modeled ??r values (0.986-0.989) were roughly consistent with the laboratory-derived values, but larger (i.e., less fractionation) than ??r values typically reported for enzyme-limited respiration in open water environments. Because of large diel variation in O2, P:R could not be estimated by directly applying the typical steady-state solution to the O2 and 18O-O2 mass balance equations in the absence of gas transfer data. Instead, our results indicate that a modified steady-state solution (the daily mean value approach) could be used with time-averaged O2 and ??18O2 measurements to calculate P:R independent of gas transfer. This approach was applicable under specifically defined, net heterotrophic conditions. The diel cycle of increasing daytime R and decreasing nighttime R was only partially explained by temperature variation, but could be consistent with the diel production/consumption of labile dissolved organic carbon from photosynthesis. ?? 2007, by the American Society of Limnology and Oceanography, Inc.
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.
Irwin, E.R.; Noble, R.L.
2000-01-01
We used prepositioned area electrofishers (PAEs, 10X1.5 m) to assess diel differences in distribution of age-0 largemouth bass, Micropterus salmoides, in August 1992-1993 in a paired sampling design. PAEs were placed parallel to shore in an embayment of an unvegetated reservoir (B. E. Jordan Lake, North Carolina, USA). The catch per unit effort (CPUE=fish/PAE) was significantly higher at night than during the day in both years, indicating that age-0 largemouth bass exhibit nocturnal inshore movements. Age-0 largemouth bass captured inshore during day were smaller than those captured at night, indicating that movement patterns may change ontogenetically. Inshore-offshore movements of age-0 largemouth bass were significantly reduced in the presence of cover, suggesting that diel movements were influenced by specific habitat components. Diel movements likely were related to foraging, resting and predator avoidance behavior and could affect population dynamics and introduce bias in assessment programs.
Diel biogeochemical processes in terrestrial waters
Nimick, David A.; Gammons, Christopher H.
2011-01-01
Many biogeochemical processes in rivers and lakes respond to the solar photocycle and produce persistent patterns of measureable phenomena that exhibit a day–night, or 24-h, cycle. Despite a large body of recent literature, the mechanisms responsible for these diel fluctuations are widely debated, with a growing consensus that combinations of physical, chemical, and biological processes are involved. These processes include streamflow variation, photosynthesis and respiration, plant assimilation, and reactions involving photochemistry, adsorption and desorption, and mineral precipitation and dissolution. Diel changes in streamflow and water properties such as temperature, pH, and dissolved oxygen concentration have been widely recognized, and recently, diel studies have focused more widely by considering other constituents such as dissolved and particulate trace metals, metalloids, rare earth elements, mercury, organic matter, dissolved inorganic carbon (DIC), and nutrients. The details of many diel processes are being studied using stable isotopes, which also can exhibit diel cycles in response to microbial metabolism, photosynthesis and respiration, or changes in phase, speciation, or redox state. In addition, secondary effects that diel cycles might have, for example, on biota or in the hyporheic zone are beginning to be considered.This special issue is composed primarily of papers presented at the topical session “Diurnal Biogeochemical Processes in Rivers, Lakes, and Shallow Groundwater” held at the annual meeting of the Geological Society of America in October 2009 in Portland, Oregon. This session was organized because many of the growing number of diel studies have addressed just a small part of the full range of diel cycling phenomena found in rivers and lakes. This limited focus is understandable because (1) fundamental aspects of many diel processes are poorly understood and require detailed study, (2) the interests and expertise of individual scientists typically do not encompass the wide diversity and range of processes that produce diel cycles, and (3) the logistics of making field measurements for 24-h periods has limited recognition and understanding of these important cycles. Thus, the topical session brought together hydrologists, biologists, geochemists, and ecologists to discuss field studies, laboratory experiments, theoretical modeling, and measurement techniques related to diel cycling. Hopefully with the cross-disciplinary synergy developed at the session as well as by this special issue, a more comprehensive understanding of the interrelationships between the diel processes will be developed. Needless to say, understanding diel processes is critical for regulatory agencies and the greater scientific community. And perhaps more importantly, expanded knowledge of biogeochemical cycling may lead to better predictions of how aquatic ecosystems might react to changing conditions of contaminant loading, eutrophication, climate change, drought, industrialization, development, and other variables.
Diel variation in fig volatiles across syconium development: making sense of scents.
Borges, Renee M; Bessière, Jean-Marie; Ranganathan, Yuvaraj
2013-05-01
Plants produce volatile organic compounds (VOCs) in a variety of contexts that include response to abiotic and biotic stresses, attraction of pollinators and parasitoids, and repulsion of herbivores. Some of these VOCs may also exhibit diel variation in emission. In Ficus racemosa, we examined variation in VOCs released by fig syconia throughout syconium development and between day and night. Syconia are globular enclosed inflorescences that serve as developing nurseries for pollinating and parasitic fig wasps. Syconia are attacked by gallers early in their development, serviced by pollinators in mid phase, and are attractive to parasitoids in response to the development of gallers at later stages. VOC bouquets of the different development phases of the syconium were distinctive, as were their day and night VOC profiles. VOCs such as α-muurolene were characteristic of the pollen-receptive diurnal phase, and may serve to attract the diurnally-active pollinating wasps. Diel patterns of release of volatiles could not be correlated with their predicted volatility as determined by Henry's law constants at ambient temperatures. Therefore, factors other than Henry's law constant such as stomatal conductance or VOC synthesis must explain diel variation in VOC emission. A novel use of weighted gene co-expression network analysis (WGCNA) on the volatilome resulted in seven distinct modules of co-emitted VOCs that could be interpreted on the basis of syconium ecology. Some modules were characterized by the response of fig syconia to early galling by parasitic wasps and consisted largely of green leaf volatiles (GLVs). Other modules, that could be characterized by a combination of syconia response to oviposition and tissue feeding by larvae of herbivorous galler pollinators as well as of parasitized wasps, consisted largely of putative herbivore-induced plant volatiles (HIPVs). We demonstrated the usefulness of WGCNA analysis of the volatilome in making sense of the scents produced by the syconia at different stages and diel phases of their development.
Diel changes in metal concentrations in a geogenically acidic river: Rio Agrio, Argentina
NASA Astrophysics Data System (ADS)
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.
Song, Weimin; Chen, Shiping; Zhou, Yadan; Wu, Bo; Zhu, Yajuan; Lu, Qi; Lin, Guanghui
2015-01-01
Diel hysteresis occurs often between soil CO2 efflux (RS) and temperature, yet, little is known if diel hysteresis occurs in the two components of RS, i.e., autotrophic respiration (RA) and heterotrophic respiration (RH), and how diel hysteresis will respond to future rainfall change. We conducted a field experiment in a desert ecosystem in northern China simulating five different scenarios of future rain regimes. Diel variations of soil CO2 efflux and soil temperature were measured on Day 6 and Day 16 following the rain addition treatments each month during the growing season. We found contrasting responses in the diel hysteresis of RA and RH to soil temperature, with a clockwise hysteresis loop for RH but a counter-clockwise hysteresis loop for RA. Rain addition significantly increased the magnitude of diel hysteresis for both RH and RA on Day 6, but had no influence on either on Day 16 when soil moisture was much lower. These findings underline the different roles of biological (i.e. plant and microbial activities) and physical-chemical (e.g. heat transport and inorganic CO2 exchange) processes in regulating the diel hysteresis of RA and RH, which should be considered when estimating soil CO2 efflux in desert regions under future rainfall regime. PMID:26615895
Hamisi, Mariam; Díez, Beatriz; Lyimo, Thomas; Ininbergs, Karolina; Bergman, Birgitta
2013-06-01
Seagrasses are photoautotrophic, ecologically important components of many globally widespread coastal ecosystems, in which combined nitrogen may limit their production. We examined the biodiversity and diazotrophic capacity of microbial epiphytes associated with the phyllosphere of the seagrass Cymodocea rotundata of the Western Indian Ocean. Light microscopy, 16S rRNA and nifH gene analysis revealed the dominance of cyanobacteria in the epiphytic microbial community. Most phylotypes were related to free-living uncultured benthic cyanobacteria, while some to cyanobacterial endosymbionts of marine diatoms. Novel and potentially diazotrophic species, some of known pantropical distribution, were also discovered. Significant diel nitrogenase activities (acetylene reduction assay) were recorded (up to 358 ± 232 nmol C2H4 g(-1) of seagrass FW h(-1)). The nifH gene expression patterns showed that heterocystous phylotypes may be the dominant diazotrophs during the day and non-heterocystous at night. These data show that C. rotundata is colonized by diverse diazotrophic cyanobacteria species and suggest that these may be beneficial partners of seagrasses in nitrogen-depleted waters. © 2013 John Wiley & Sons Ltd and Society for Applied Microbiology.
Computational design of an enzyme catalyst for a stereoselective bimolecular Diels-Alder reaction
Siegel, Justin B.; Zanghellini, Alexandre; Lovick, Helena M.; Kiss, Gert; Lambert, Abigail R.; St.Clair, Jennifer L.; Gallaher, Jasmine L.; Hilvert, Donald; Gelb, Michael H.; Stoddard, Barry L.; Houk, Kendall N.; Michael, Forrest E.; Baker, David
2011-01-01
The Diels-Alder reaction is a cornerstone in organic synthesis, forming two carbon-carbon bonds and up to four new stereogenic centers in one step. No naturally occurring enzymes have been shown to catalyze bimolecular Diels-Alder reactions. We describe the de novo computational design and experimental characterization of enzymes catalyzing a bimolecular Diels-Alder reaction with high stereoselectivity and substrate specificity. X-ray crystallography confirms that the structure matches the design for the most active of the enzymes, and binding site substitutions reprogram the substrate specificity. Designed stereoselective catalysts for carbon-carbon bond forming reactions should be broadly useful in synthetic chemistry. PMID:20647463
Computational design of an enzyme catalyst for a stereoselective bimolecular Diels-Alder reaction.
Siegel, Justin B; Zanghellini, Alexandre; Lovick, Helena M; Kiss, Gert; Lambert, Abigail R; St Clair, Jennifer L; Gallaher, Jasmine L; Hilvert, Donald; Gelb, Michael H; Stoddard, Barry L; Houk, Kendall N; Michael, Forrest E; Baker, David
2010-07-16
The Diels-Alder reaction is a cornerstone in organic synthesis, forming two carbon-carbon bonds and up to four new stereogenic centers in one step. No naturally occurring enzymes have been shown to catalyze bimolecular Diels-Alder reactions. We describe the de novo computational design and experimental characterization of enzymes catalyzing a bimolecular Diels-Alder reaction with high stereoselectivity and substrate specificity. X-ray crystallography confirms that the structure matches the design for the most active of the enzymes, and binding site substitutions reprogram the substrate specificity. Designed stereoselective catalysts for carbon-carbon bond-forming reactions should be broadly useful in synthetic chemistry.
Fe(II)/Fe(III)-Catalyzed Intramolecular Didehydro-Diels-Alder Reaction of Styrene-ynes.
Mun, Hyeon Jin; Seong, Eun Young; Ahn, Kwang-Hyun; Kang, Eun Joo
2018-02-02
The intramolecular didehydro-Diels-Alder reaction of styrene-ynes was catalyzed by Fe(II) and Fe(III) to produce various naphthalene derivatives under microwave heating conditions. Mechanistic calculations found that the Fe(II) catalyst activates the styrenyl diene in an inverse-electron-demand Diels-Alder reaction, and the consecutive dehydrogenation reaction can be promoted by either Fe(II)-catalyzed direct dehydrogenation or an Fe(III)-catalyzed rearomatization/dehydrogenation pathway.
NASA Astrophysics Data System (ADS)
Lillis, Ashlee; Mooney, T. Aran
2018-06-01
The rich acoustic environment of coral reefs, including the sounds of a variety of fish and invertebrates, is a reflection of the structural complexity and biological diversity of these habitats. Emerging interest in applying passive acoustic monitoring and soundscape analysis to measure coral reef habitat characteristics and track ecological patterns is hindered by a poor understanding of the most common and abundant sound producers on reefs—the snapping shrimp. Here, we sought to address several basic biophysical drivers of reef sound by investigating acoustic activity patterns of snapping shrimp populations on two adjacent coral reefs using a detailed snap detection analysis routine to a high-resolution 2.5-month acoustic dataset from the US Virgin Islands. The reefs exhibited strong diel and lunar periodicity in snap rates and clear spatial differences in snapping levels. Snap rates peaked at dawn and dusk and were higher overall during daytime versus nighttime, a seldom-reported pattern in earlier descriptions of diel snapping shrimp acoustic activity. Small differences between the sites in snap rate rhythms were detected and illustrate how analyses of specific soundscape elements might reveal subtle between-reef variation. Snap rates were highly correlated with environmental variables, including water temperature and light, and were found to be sensitive to changes in oceanographic forcing. This study further establishes snapping shrimp as key players in the coral reef chorus and provides evidence that their acoustic output reflects a combination of environmental conditions, celestial influences, and spatial habitat variation. Effective application of passive acoustic monitoring in coral reef habitats using snap rates or snapping-influenced acoustic metrics will require a mechanistic understanding of the underlying spatial and temporal variation in snapping shrimp sound production across multiple scales.
Baumann, Hannes; Wallace, Ryan; Tagliaferri, Tristen N.; Gobler, Christopher J.
2014-01-01
Coastal marine organisms experience dynamic pH and dissolved oxygen (DO) conditions in their natural habitats, which may impact their susceptibility to long-term anthropogenic changes. Robust characterizations of all temporal scales of natural pH and DO fluctuations in different marine habitats are needed; however, appropriate time series of pH and DO are still scarce. We used multiyear (2008–2012), high-frequency (6 min) monitoring data to quantify diel, seasonal, and interannual scales of pH and DO variability in a productive, temperate tidal salt marsh (Flax Pond, Long Island, US). pHNBS and DO showed strong and similar seasonal patterns, with average (minimum) conditions declining from 8.2 (8.1) and 12.5 (11.4) mg l−1 at the end of winter to 7.6 (7.2) and 6.3 (2.8) mg l−1 in late summer, respectively. Concomitantly, average diel fluctuations increased from 0.22 and 2.2 mg l−1 (February) to 0.74 and 6.5 mg l−1 (August), respectively. Diel patterns were modulated by tides and time of day, eliciting the most extreme minima when low tides aligned with the end of the night. Simultaneous in situ pCO2 measurements showed striking fluctuations between ∼330 and ∼1,200 (early May), ∼2,200 (mid June), and ∼4,000 μatm (end of July) within single tidal cycles. These patterns also indicate that the marsh’s strong net heterotrophy influences its adjacent estuary by ‘outwelling’ acidified and hypoxic water during ebb tides. Our analyses emphasize the coupled and fluctuating nature of pH and DO conditions in productive coastal and estuarine environments, which have yet to be adequately represented by experiments.
Passive Autonomous Acoustic Monitoring of Marine Mammals with Seagliders
2012-09-30
programmed to hold its position on top of the Whiskey 1 array (’stationary glider’) while the second glider (’transecting glider’) conducted East...tagged beaked whale (black dot). 7 c) Dolphins and sperm whales diving activity has a significant diel pattern (Fig. 4). There is a hint that...Am. 129(6):3610-3622. Mellinger, D.K., K.M. Stafford, and C.G. Fox. 2004. Seasonal occurrence of sperm whale (Physeter macrocephalus) sounds in the
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 functional annotation.
NASA Astrophysics Data System (ADS)
Durbin, Edward G.; Gilman, Sharon L.; Campbell, Robert G.; Durbin, Ann G.
Abundance, biomass, diel vertical migration and estimated in situ development in the copepod Calanus finmarchicus were investigated during late spring in 1988 and 1989 in the southern Gulf of Maine. This region is an important feeding ground for the planktivorous right whale, Eubalaena glacialis. The 1988 study took place during the declining spring bloom, with phytoplankton biomass variable, but relatively high. The 1989 study occurred after seasonal stratification, and phytoplankton biomass was low. During the 1988 cruise the dominant stage in C. finmarchicus shifted from C1-C2 to C4-C5. Stage durations during 1988 (4.0 days for C3 and 6.6 days for C4), estimated from the temporal change in stage distribution, were similar to maximal values observed in the laboratory. In contrast, during 1989 stages C4 and C5 were dominant throughout the study period and development rate was slow (estimated C4 stage duration about 24 days). Diel vertical migration patterns changed, from an absence of migration at the first two 1988 stations where younger stages predominated (C1-C3), to a very strong diel vertical migration at the later 1988 stations where stages C3-C3 predominated. This was not a simple ontogenetic change in migratory behavior since all copepodite stages at each station showed similar patterns. During 1989 dense aggregations of C. finmarchicus remained in the surface layer both day and night, and no diel vertical migration was observed. A small, nonmigratory population of late-stage C. finmarchicus was found at depth. Individual body size of these copepods was considerably greater than those found at the surface. Differences in development rate between years reflect differences in the food environment, brought about by seasonal hydrographic changes and the development of more intense stratification. Diel vertical migration patterns, however, did not show a simple relation with food availability, and it is suggested that predation may play an important role in regulating the behavior of the copepods.
Contrasting Fish Behavior in Artificial Seascapes with Implications for Resources Conservation
Koeck, Barbara; Alós, Josep; Caro, Anthony; Neveu, Reda; Crec'hriou, Romain; Saragoni, Gilles; Lenfant, Philippe
2013-01-01
Artificial reefs are used by many fisheries managers as a tool to mitigate the impact of fisheries on coastal fish communities by providing new habitat for many exploited fish species. However, the comparison between the behavior of wild fish inhabiting either natural or artificial habitats has received less attention. Thus the spatio-temporal patterns of fish that establish their home range in one habitat or the other and their consequences of intra-population differentiation on life-history remain largely unexplored. We hypothesize that individuals with a preferred habitat (i.e. natural vs. artificial) can behave differently in terms of habitat use, with important consequences on population dynamics (e.g. life-history, mortality, and reproductive success). Therefore, using biotelemetry, 98 white seabream (Diplodus sargus) inhabiting either artificial or natural habitats were tagged and their behavior was monitored for up to eight months. Most white seabreams were highly resident either on natural or artificial reefs, with a preference for the shallow artificial reef subsets. Connectivity between artificial and natural reefs was limited for resident individuals due to great inter-habitat distances. The temporal behavioral patterns of white seabreams differed between artificial and natural reefs. Artificial-reef resident fish had a predominantly nocturnal diel pattern, whereas natural-reef resident fish showed a diurnal diel pattern. Differences in diel behavioral patterns of white seabream inhabiting artificial and natural reefs could be the expression of realized individual specialization resulting from differences in habitat configuration and resource availability between these two habitats. Artificial reefs have the potential to modify not only seascape connectivity but also the individual behavioral patterns of fishes. Future management plans of coastal areas and fisheries resources, including artificial reef implementation, should therefore consider the potential effect of habitat modification on fish behavior, which could have key implications on fish dynamics. PMID:23935978
Contrasting fish behavior in artificial seascapes with implications for resources conservation.
Koeck, Barbara; Alós, Josep; Caro, Anthony; Neveu, Reda; Crec'hriou, Romain; Saragoni, Gilles; Lenfant, Philippe
2013-01-01
Artificial reefs are used by many fisheries managers as a tool to mitigate the impact of fisheries on coastal fish communities by providing new habitat for many exploited fish species. However, the comparison between the behavior of wild fish inhabiting either natural or artificial habitats has received less attention. Thus the spatio-temporal patterns of fish that establish their home range in one habitat or the other and their consequences of intra-population differentiation on life-history remain largely unexplored. We hypothesize that individuals with a preferred habitat (i.e. natural vs. artificial) can behave differently in terms of habitat use, with important consequences on population dynamics (e.g. life-history, mortality, and reproductive success). Therefore, using biotelemetry, 98 white seabream (Diplodus sargus) inhabiting either artificial or natural habitats were tagged and their behavior was monitored for up to eight months. Most white seabreams were highly resident either on natural or artificial reefs, with a preference for the shallow artificial reef subsets. Connectivity between artificial and natural reefs was limited for resident individuals due to great inter-habitat distances. The temporal behavioral patterns of white seabreams differed between artificial and natural reefs. Artificial-reef resident fish had a predominantly nocturnal diel pattern, whereas natural-reef resident fish showed a diurnal diel pattern. Differences in diel behavioral patterns of white seabream inhabiting artificial and natural reefs could be the expression of realized individual specialization resulting from differences in habitat configuration and resource availability between these two habitats. Artificial reefs have the potential to modify not only seascape connectivity but also the individual behavioral patterns of fishes. Future management plans of coastal areas and fisheries resources, including artificial reef implementation, should therefore consider the potential effect of habitat modification on fish behavior, which could have key implications on fish dynamics.
2011-09-30
endangered baleen whale species, the humpback whale (Megaptera novaengliae) and the right whale (Eubalaena glacialis), on the Stellwagen Bank National...in dive profiles and horizontal movement patterns for tagged humpback and right whales on the Stellwagen Bank National Marine Sanctuary; 2...determine the sound production behavior of individual tagged humpback and right whales on the Stellwagen Bank National Marine Sanctuary; and 3) examine the
Diel behavior of rearing fall Chinook salmon
Tiffan, Kenneth F.; Kock, Tobias J.; Skalicky, Joseph J.
2010-01-01
In fisheries science, habitat use is often inferred when fish are sampled or observed in a particular location. Physical habitat is typically measured where fish are found, and thus deemed important to habitat use. Although less common, a more informative approach is to measure or observe fish behavior within given habitats to more thoroughly assess their use of those locations. While this approach better reflects how fish use habitat, fish behavior can be difficult to quantify, particularly at night. For example, Tiffan and others (2002, 2006) were able to quantify habitat availability and characteristics that were important for rearing juvenile fall Chinook Salmon (Oncorhynchus tshawytscha) in the Hanford Reach of the Columbia River. The authors, however, could only speculate as to how juvenile salmon use habitat and respond to changes in water level fluctuations. Conversely, in this study we provide data on the diel activities of rearing juvenile wild fall Chinook Salmon which provides a better understanding of how fish “use” these rearing habitats. Diel behavior patterns are important because fish in the Hanford Reach are often stranded on shorelines when the water level rapidly recedes because of hydroelectric power generation at upriver dams (Nugent and others 2002; Anglin and others 2006). We hypothesize that juvenile salmon are at greater risk of stranding at night because they are less active and occupy habitat differently than during the day. We used underwater videography to collect behavioral information during the day and night to determine if juvenile fall Chinook Salmon are more susceptible to stranding when water level fluctuations occur at night.
DIEL OXYGEN-INDUCED MOVEMENT OF FISH ASSEMBLAGES IN A GREAT LAKES COASTAL WETLAND
To determine the importance of dissolved oxygen conditions in influencing daily ovement patterns of fishes in Great Lakes coastal wetlands, we sampled migrating fish assemblages from habitats with varying diurnal dissolved oxygen patterns in a Lake Superior coastal wetland during...
Diel feeding periodicity of Ephemera simulans nymphs in summer and winter
Johnson, James H.; Ruggirello, Jack E.; Nack, Christopher C.
2012-01-01
We examined diel feeding periodicity of Ephemera simulans nymphs during summer and winter in a third-order stream in central New York. A total of 245 nymphs were collected at 4-h intervals over two 24 h periods and were immediately preserved in 80% ethanol. In the laboratory, we weighed each nymph and its digestive tract. The ratio of wet weight of the digestive tract to the total body weight at each 4-h interval was used to determine feeding periodicity. Diel feeding periodicity followed a similar pattern in summer and winter and was significantly higher at 08:00 hours. Feeding periodicity of E. simulans in Labrador Creek is asynchronous with the two most abundant fish species in the stream and may reflect predator avoidance behavior that has been shown for other mayfly species.
Kirschner, A K T; Eiler, A; Zechmeister, T C; Velimirov, B; Herzig, A; Mach, R; Farnleitner, A H
2002-09-01
Diel changes in bacterial and cyanobacterial numbers, as well as heterotrophic bacterial production, were examined in two shallow alkaline pools, harbouring dense populations of cyanobacteria (up to 1100 x 109 cells l-1) and bacteria (up to 500 x 109 cells l-1). Together with the recorded bacterial production rates (925 micro gC l-1x h-1), these values are the highest reported for natural aquatic ecosystems. The investigations were performed during a fair-weather situation, and during a rapid change after a long-term fair-weather situation to thunderstorms and heavy rainfall. During fair weather, bacterial growth was significantly correlated to the diurnal light and temperature cycle. Prokaryotic abundances were fairly constant, and loss by grazing and viral lysis must have been of significant importance. During the invasion of rainy weather, the prokaryotic community showed a strong and immediate response. A significant enhancement of bacterial growth followed after rainfall, suggesting that the high salt concentrations had inhibited bacterial activity. Changes in bacterial and cyanobacterial numbers were consistent with this pattern. From comparison with the available literature, we conclude that diel changes of bacterioplankton are regulated by a complex combination of environmental factors specific for each investigated ecosystem. In the soda pools investigated, external abiotic factors were dominant on a diel scale. In larger ecosystems, such factors are much more buffered and internal biotic interactions may prevail.
Johannsson, O E; Bergman, H L; Wood, C M; Laurent, P; Kavembe, D G; Bianchini, A; Maina, J N; Chevalier, C; Bianchini, L F; Papah, M B; Ojoo, R O
2014-03-01
Observations of the Magadi tilapia Alcolapia grahami in hot, highly alkaline Lake Magadi revealed that they air breathe not only during hypoxia, as described previously, but also during normoxia and hyperoxia. Air breathing under these latter conditions occurred within distinct groupings of fish (pods) and involved only a small proportion of the population. Air breathing properties (duration and frequency) were quantified from video footage. Air breathing within the population followed a diel pattern with the maximum extent of pod formation occurring in early afternoon. High levels of reactive oxygen species (ROS) in the water may be an irritant that encourages the air-breathing behaviour. The diel pattern of air breathing in the field and in experiments followed the diel pattern of ROS concentrations in the water which are amongst the highest reported in the literature (maximum daytime values of 2.53 – 8.10 μM H₂O₂). Interlamellar cell masses (ILCM) occurred between the gill lamellae of fish from the lagoon with highest ROS and highest oxygen levels, while fish from a normoxic lagoon with one third the ROS had little or no ILCM. This is the first record of air breathing in a facultative air-breathing fish in hyperoxic conditions and the first record of an ILCM in a cichlid species. © 2013 The Fisheries Society of the British Isles.
Townsend, Steven D.; Wu, Xiangyang; Danishefsky, Samuel J.
2012-01-01
α,β-Unsaturated imides, formylated at the nitrogen atom, comprise a new and valuable family of dienophiles for servicing Diels-Alder reactions. These systems are assembled through extension of recently discovered isonitrile chemistry to the domain of α,β-unsaturated acids. Cycloadditions are facilitated by Et2AlCl, presumably via chelation between the two carbonyl groups of the N-formyl amide. Applications of the isonitrile/Diels-Alder logic to the IMDA reaction, as well as methodologies to modify the N-formyl amide of the resultant cycloaddition product, are described. It is expected that this easily executed chemistry will provide a significant enhancement for application of Diels-Alder reactions to many synthetic targets. PMID:22708980
Behavioural Thermoregulatory Tactics in Lacustrine Brook Charr, Salvelinus fontinalis
Bertolo, Andrea; Pépino, Marc; Adams, Julie; Magnan, Pierre
2011-01-01
The need to vary body temperature to optimize physiological processes can lead to thermoregulatory behaviours, particularly in ectotherms. Despite some evidence of within-population phenotypic variation in thermal behaviour, the occurrence of alternative tactics of this behaviour is rarely explicitly considered when studying natural populations. The main objective of this study was to determine whether different thermal tactics exist among individuals of the same population. We studied the behavioural thermoregulation of 33 adult brook charr in a stratified lake using thermo-sensitive radio transmitters that measured hourly individual temperature over one month. The observed behavioural thermoregulatory patterns were consistent between years and suggest the existence of four tactics: two “warm” tactics with both crepuscular and finer periodicities, with or without a diel periodicity, and two “cool” tactics, with or without a diel periodicity. Telemetry data support the above findings by showing that the different tactics are associated with different patterns of diel horizontal movements. Taken together, our results show a clear spatio-temporal segregation of individuals displaying different tactics, suggesting a reduction of niche overlap. To our knowledge, this is the first study showing the presence of behavioural thermoregulatory tactics in a vertebrate. PMID:21490935
Hinrichs, Saskia; Patten, Nicole L.; Waite, Anya M.
2013-01-01
Coral health indices are important components of the management assessments of coral reefs, providing insight into local variation in reef condition, as well as tools for comparisons between reefs and across various time scales. Understanding how such health indices vary in space and time is critical to their successful implementation as management tools. Here we compare autotrophic and heterotrophic coral health indices, examining specifically the temporal variation driven by the local environmental variation, at three scales (diel, daily and seasonal). We compared metabolic indices (RNA/DNA ratio, protein concentration) and autotrophic indices (Chlorophyll a (Chl a), zooxanthellae density, effective quantum yield (yield) and relative electron transport rate (rETR)) for two dominant Acropora species, A. digitifera and A. spicifera at Ningaloo Reef (north-western Australia) in August 2010 (austral winter) and February 2011 (austral summer). Clear seasonal patterns were documented for metabolic indices, zooxanthellae density and rETR, while cyclic diel patterns only occurred for yield and rETR, and RNA/DNA ratio. Significant daily variation was observed for RNA/DNA ratio, Chl a concentration, yield and rETR. Results suggest that zooxanthellae density and protein concentrations are good long-term indicators of coral health whose variance is largely seasonal, while RNA/DNA ratio and rETR can be used for both long-term (seasonal) and short-term (diel) coral monitoring. Chl a can be used to describe changes between days and yield for both diel and daily variations. Correlations between health indices and light history showed that short-term changes in irradiance had the strongest impact on all health indices except zooxanthellae density for A. digitifera; for A. spicifera no correlation was observed at all. However, cumulative irradiance over the several days before sampling showed significant correlations with most health indices suggesting that a time-lag effect has to be taken into account when interpreting diel variations in coral condition. PMID:23696848
Hinrichs, Saskia; Patten, Nicole L; Waite, Anya M
2013-01-01
Coral health indices are important components of the management assessments of coral reefs, providing insight into local variation in reef condition, as well as tools for comparisons between reefs and across various time scales. Understanding how such health indices vary in space and time is critical to their successful implementation as management tools. Here we compare autotrophic and heterotrophic coral health indices, examining specifically the temporal variation driven by the local environmental variation, at three scales (diel, daily and seasonal). We compared metabolic indices (RNA/DNA ratio, protein concentration) and autotrophic indices (Chlorophyll a (Chl a), zooxanthellae density, effective quantum yield (yield) and relative electron transport rate (rETR)) for two dominant Acropora species, A. digitifera and A. spicifera at Ningaloo Reef (north-western Australia) in August 2010 (austral winter) and February 2011 (austral summer). Clear seasonal patterns were documented for metabolic indices, zooxanthellae density and rETR, while cyclic diel patterns only occurred for yield and rETR, and RNA/DNA ratio. Significant daily variation was observed for RNA/DNA ratio, Chl a concentration, yield and rETR. Results suggest that zooxanthellae density and protein concentrations are good long-term indicators of coral health whose variance is largely seasonal, while RNA/DNA ratio and rETR can be used for both long-term (seasonal) and short-term (diel) coral monitoring. Chl a can be used to describe changes between days and yield for both diel and daily variations. Correlations between health indices and light history showed that short-term changes in irradiance had the strongest impact on all health indices except zooxanthellae density for A. digitifera; for A. spicifera no correlation was observed at all. However, cumulative irradiance over the several days before sampling showed significant correlations with most health indices suggesting that a time-lag effect has to be taken into account when interpreting diel variations in coral condition.
Angermayr, S. Andreas; van Alphen, Pascal; Hasdemir, Dicle; Kramer, Gertjan; Iqbal, Muzamal; van Grondelle, Wilmar; Hoefsloot, Huub C.; Choi, Young Hae
2016-01-01
ABSTRACT Investigating the physiology of cyanobacteria cultured under a diel light regime is relevant for a better understanding of the resulting growth characteristics and for specific biotechnological applications that are foreseen for these photosynthetic organisms. Here, we present the results of a multiomics study of the model cyanobacterium Synechocystis sp. strain PCC 6803, cultured in a lab-scale photobioreactor in physiological conditions relevant for large-scale culturing. The culture was sparged with N2 and CO2, leading to an anoxic environment during the dark period. Growth followed the availability of light. Metabolite analysis performed with 1H nuclear magnetic resonance analysis showed that amino acids involved in nitrogen and sulfur assimilation showed elevated levels in the light. Most protein levels, analyzed through mass spectrometry, remained rather stable. However, several high-light-response proteins and stress-response proteins showed distinct changes at the onset of the light period. Microarray-based transcript analysis found common patterns of ∼56% of the transcriptome following the diel regime. These oscillating transcripts could be grouped coarsely into genes that were upregulated and downregulated in the dark period. The accumulated glycogen was degraded in the anaerobic environment in the dark. A small part was degraded gradually, reflecting basic maintenance requirements of the cells in darkness. Surprisingly, the largest part was degraded rapidly in a short time span at the end of the dark period. This degradation could allow rapid formation of metabolic intermediates at the end of the dark period, preparing the cells for the resumption of growth at the start of the light period. IMPORTANCE Industrial-scale biotechnological applications are anticipated for cyanobacteria. We simulated large-scale high-cell-density culturing of Synechocystis sp. PCC 6803 under a diel light regime in a lab-scale photobioreactor. In BG-11 medium, Synechocystis grew only in the light. Metabolite analysis grouped the collected samples according to the light and dark conditions. Proteome analysis suggested that the majority of enzyme-activity regulation was not hierarchical but rather occurred through enzyme activity regulation. An abrupt light-on condition induced high-light-stress proteins. Transcript analysis showed distinct patterns for the light and dark periods. Glycogen gradually accumulated in the light and was rapidly consumed in the last quarter of the dark period. This suggests that the circadian clock primed the cellular machinery for immediate resumption of growth in the light. PMID:27208121
Vertical migrations of a deep-sea fish and its prey.
Afonso, Pedro; McGinty, Niall; Graça, Gonçalo; Fontes, Jorge; Inácio, Mónica; Totland, Atle; Menezes, Gui
2014-01-01
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.
Stöckl, Anna L; Kihlström, Klara; Chandler, Steven; Sponberg, Simon
2017-04-05
Flight control in insects is heavily dependent on vision. Thus, in dim light, the decreased reliability of visual signal detection also prompts consequences for insect flight. We have an emerging understanding of the neural mechanisms that different species employ to adapt the visual system to low light. However, much less explored are comparative analyses of how low light affects the flight behaviour of insect species, and the corresponding links between physiological adaptations and behaviour. We investigated whether the flower tracking behaviour of three hawkmoth species with different diel activity patterns revealed luminance-dependent adaptations, using a system identification approach. We found clear luminance-dependent differences in flower tracking in all three species, which were explained by a simple luminance-dependent delay model, which generalized across species. We discuss physiological and anatomical explanations for the variance in tracking responses, which could not be explained by such simple models. Differences between species could not be explained by the simple delay model. However, in several cases, they could be explained through the addition on a second model parameter, a simple scaling term, that captures the responsiveness of each species to flower movements. Thus, we demonstrate here that much of the variance in the luminance-dependent flower tracking responses of hawkmoths with different diel activity patterns can be captured by simple models of neural processing.This article is part of the themed issue 'Vision in dim light'. © 2017 The Author(s).
Nakamura, Maya; Wright, Jonathan C
2013-01-01
A key evolutionary development facilitating land colonization in terrestrial isopods (Isopoda: Oniscidea) is the intermittent liberation of waste nitrogen as volatile ammonia. Intermittent ammonia release exploits glutamine (Gln) as an intermediary nitrogen store. Here, we explore the relationship between temporal patterns of ammonia release and Gln accumulation in three littoral oniscideans from Southern California. Results are interpreted in terms of water availability, habitat, activity patterns, and ancestry. A two-way experimental design was used to test whether ammonia excretion and Gln accumulation follow a tidal or diel periodicity. Ammonia excretion was studied in the laboratory using chambers with or without available seawater and using an acid trap to collect volatile ammonia. Ligia occidentalis releases ammonia directly into seawater and accumulates Gln during low tide (48.9 ± 6.5 μmol g⁻¹ at low tide, 24.1 ± 3.0 μmol g⁻¹ at high tide), indicating that excretion is tidally constrained. Alloniscus perconvexus and Tylos punctatus can excrete ammonia directly into seawater or utilize volatilization. Both species burrow in sand by day and show a diel excretory pattern, accumulating Gln nocturnally (31.8 ± 2.7 μmol g⁻¹ at dawn and 21.8 ± 2.3 μmol g⁻¹ at dusk for A. perconvexus; 85.7 ± 15.1 μmol g⁻¹ at dawn and 25.4 ± 2.9 μmol g⁻¹ at dusk for T. punctatus) and liberating ammonia diurnally. Glutaminase shows higher activity in terrestrial (0.54-0.86 U g⁻¹) compared to intertidal (0.25-0.31 U g⁻¹) species, consistent with the need to generate high PNH₃ for volatilization. The predominant isoform in Armadillidium vulgare is phosphate dependent and maleate independent; phosphate is a plausible regulator in vivo.
Jones, Clain A.; Nimick, D.A.; McCleskey, R. Blaine
2004-01-01
Diel (24 hr) cycles in dissolved metal and As concentrations have been documented in many northern Rocky Mountain streams in the U.S.A. The cause(s) of the cycles are unknown, although temperature- and pH-dependent sorption reactions have been cited as likely causes. A light/dark experiment was conducted to isolate temperature and pH as variables affecting diel metal cycles in Prickly Pear Creek, Montana. Light and dark chambers containing sediment and a strand of macrophyte were placed in the stream to simulate instream temperature oscillations. Photosynthesis-induced pH changes were allowed to proceed in the light chambers while photosynthesis was prevented in the dark chambers. Water samples were collected periodically for 22 hr in late July 2001 from all chambers and the stream. In the stream, dissolved Zn concentrations increased by 300% from late afternoon to early morning, while dissolved As concentrations exhibited the opposite pattern, increasing 33% between early morning and late afternoon. Zn and As concentrations in the light chambers showed similar, though less pronounced, diel variations. Conversely, Zn and As concentrations in the dark chambers had no obvious diel variation, indicating that light, or light-induced reactions, caused the variation. Temperature oscillations were nearly identical between light and dark chambers, strongly suggesting that temperature was not controlling the diel variations. As expected, pH was negatively correlated (P < 0.01) with dissolved Zn concentrations and positively correlated with dissolved As concentrations in both the light and dark chambers. From these experiments, photosynthesis-induced pH changes were determined to be the major cause of the diel dissolved Zn and As cycles in Prickly Pear Creek. Further research is necessary in other streams to verify that this finding is consistent among streams having large differences in trace-element concentrations and mineralogy of channel substrate. ?? 2004 Kluwer Academic Publishers.
Phylogenetic, ecological, and allometric correlates of cranial shape in Malagasy lemuriforms.
Baab, Karen L; Perry, Jonathan M G; Rohlf, F James; Jungers, William L
2014-05-01
Adaptive radiations provide important insights into many aspects of evolution, including the relationship between ecology and morphological diversification as well as between ecology and speciation. Many such radiations include divergence along a dietary axis, although other ecological variables may also drive diversification, including differences in diel activity patterns. This study examines the role of two key ecological variables, diet and activity patterns, in shaping the radiation of a diverse clade of primates, the Malagasy lemurs. When phylogeny was ignored, activity pattern and several dietary variables predicted a significant proportion of cranial shape variation. However, when phylogeny was taken into account, only typical diet accounted for a significant proportion of shape variation. One possible explanation for this discrepancy is that this radiation was characterized by a relatively small number of dietary shifts (and possibly changes in body size) that occurred in conjunction with the divergence of major clades. This pattern may be difficult to detect with the phylogenetic comparative methods used here, but may characterize not just lemurs but other mammals. © 2014 The Author(s). Evolution © 2014 The Society for the Study of Evolution.
Corcoran, Mark J; Wetherbee, Bradley M; Shivji, Mahmood S; Potenski, Matthew D; Chapman, Demian D; Harvey, Guy M
2013-01-01
Southern stingrays, Dasyatis americana, have been provided supplemental food in ecotourism operations at Stingray City Sandbar (SCS), Grand Cayman since 1986, with this site becoming one of the world's most famous and heavily visited marine wildlife interaction venues. Given expansion of marine wildlife interactive tourism worldwide, there are questions about the effects of such activities on the focal species and their ecosystems. We used a combination of acoustic telemetry and tag-recapture efforts to test the hypothesis that human-sourced supplemental feeding has altered stingray activity patterns and habitat use at SCS relative to wild animals at control sites. Secondarily, we also qualitatively estimated the population size of stingrays supporting this major ecotourism venue. Tag-recapture data indicated that a population of at least 164 stingrays, over 80% female, utilized the small area at SCS for prolonged periods of time. Examination of comparative movements of mature female stingrays at SCS and control sites revealed strong differences between the two groups: The fed animals demonstrated a notable inversion of diel activity, being constantly active during the day with little movement at night compared to the nocturnally active wild stingrays; The fed stingrays utilized significantly (p<0.05) smaller 24 hour activity spaces compared to wild conspecifics, staying in close proximity to the ecotourism site; Fed stingrays showed a high degree of overlap in their core activity spaces compared to wild stingrays which were largely solitary in the spaces utilized (72% vs. 3% overlap respectively). Supplemental feeding has strikingly altered movement behavior and spatial distribution of the stingrays, and generated an atypically high density of animals at SCS which could have downstream fitness costs for individuals and potentially broader ecosystem effects. These findings should help environmental managers plan mitigating measures for existing operations, and develop precautionary policies regarding proposed feeding sites.
Corcoran, Mark J.; Wetherbee, Bradley M.; Shivji, Mahmood S.; Potenski, Matthew D.; Chapman, Demian D.; Harvey, Guy M.
2013-01-01
Southern stingrays, Dasyatis americana, have been provided supplemental food in ecotourism operations at Stingray City Sandbar (SCS), Grand Cayman since 1986, with this site becoming one of the world’s most famous and heavily visited marine wildlife interaction venues. Given expansion of marine wildlife interactive tourism worldwide, there are questions about the effects of such activities on the focal species and their ecosystems. We used a combination of acoustic telemetry and tag-recapture efforts to test the hypothesis that human-sourced supplemental feeding has altered stingray activity patterns and habitat use at SCS relative to wild animals at control sites. Secondarily, we also qualitatively estimated the population size of stingrays supporting this major ecotourism venue. Tag-recapture data indicated that a population of at least 164 stingrays, over 80% female, utilized the small area at SCS for prolonged periods of time. Examination of comparative movements of mature female stingrays at SCS and control sites revealed strong differences between the two groups: The fed animals demonstrated a notable inversion of diel activity, being constantly active during the day with little movement at night compared to the nocturnally active wild stingrays; The fed stingrays utilized significantly (p<0.05) smaller 24 hour activity spaces compared to wild conspecifics, staying in close proximity to the ecotourism site; Fed stingrays showed a high degree of overlap in their core activity spaces compared to wild stingrays which were largely solitary in the spaces utilized (72% vs. 3% overlap respectively). Supplemental feeding has strikingly altered movement behavior and spatial distribution of the stingrays, and generated an atypically high density of animals at SCS which could have downstream fitness costs for individuals and potentially broader ecosystem effects. These findings should help environmental managers plan mitigating measures for existing operations, and develop precautionary policies regarding proposed feeding sites. PMID:23527144
Wassmann, Reiner; Alberto, Ma. Carmelita; Tirol-Padre, Agnes; Hoang, Nghia Trong; Romasanta, Ryan; Centeno, Caesar Arloo; Sander, Bjoern Ole
2018-01-01
This study comprises field experiments on methane emissions from rice fields conducted with an Eddy-Covariance (EC) system as well as test runs for a modified closed chamber approach based on measurements at nighttime. The EC data set covers 4 cropping seasons with highly resolved emission rates (raw data in 10 Hz frequency have been aggregated to 30-min records). The diel patterns were very pronounced in the two dry seasons with peak emissions at early afternoon and low emissions at nighttime. These diel patterns were observed at all growing stages of the dry seasons. In the two wet seasons, the diel patterns were only visible during the vegetative stages while emission rates during reproductive and ripening stages remained within a fairly steady range and did not show any diel patterns. In totality, however, the data set revealed a very strong linear relationship between nocturnal emissions (12-h periods) and the full 24-h periods resulting in an R2-value of 0.8419 for all data points. In the second experiment, we conducted test runs for chamber measurements at nighttime with much longer deployment times (6 h) as compared to measurements at daylight (typically for 30 min). Conducting chamber measurements at nighttime excluded drastic changes of temperatures and CO2 concentrations. The data also shows that increases in CH4 concentrations remained on linear trajectory over a 6h period at night. While end CH4 concentrations were consistently >3.5 ppm, this long-term enclosure represents a very robust approach to quantify emissions as compared to assessing short-term concentration increases over time near the analytical detection limit. Finally, we have discussed the potential applications of this new approach that would allow emission measurements even when conventional (daytime) measurements will not be suitable. Nighttime chamber measurements offer an alternative to conventional (daytime) measurements if either (i) baseline emissions are at a very low level, (ii) differences of tested crop treatments or varieties are very small or (iii) the objective is to screen a large number of rice varieties for taking advantage of progress in genome sequencing. PMID:29390000
Diel ontogenetic shift in parasitic activity in a gnathiid isopod on Caribbean coral reefs
NASA Astrophysics Data System (ADS)
Sikkel, P. C.; Ziemba, R. E.; Sears, W. T.; Wheeler, J. C.
2009-06-01
Ontogenetic niche shifts are characteristic of organisms with complex life cycles such as many marine invertebrates. Research has focused primarily on changes in habitat or diet. However, ontogenetic changes can also occur in the temporal pattern of foraging. Gnathiid isopods feed on fish blood throughout their larval stages and are the primary food item for cleaning organisms on coral reefs. At sites in Australia and the Caribbean, gnathiid larvae exhibit size-related differences in diel activity. However, it is unclear whether this is due to interspecific or intraspecific variation in behavior. Fish were deployed in cages near sunset on shallow reefs off St. John, U.S. Virgin Islands and allowed to be infected with larval gnathiids. Larvae collected from fish retrieved near midnight developed into adults, with most developing into females. In contrast, approximately 80% of gnathiids collected after first light developed into second or third stage larvae, and nearly all of the remaining, large, individuals developed into males. Comparison of ITS2 gene regions from individuals collected in emergence traps from the same reefs during the day versus during the night revealed no differences in this highly variable region. Thus, gnathiid larvae at this locality shift their time of activity as they develop, and larvae developing into males remain active over a longer time period than those developing into females.
Weiss, Julia; Terry, Marta I; Martos-Fuentes, Marina; Letourneux, Lisa; Ruiz-Hernández, Victoria; Fernández, Juan A; Egea-Cortines, Marcos
2018-02-14
Cowpea (Vigna unguiculata) is an important source of protein supply for animal and human nutrition. The major storage globulins VICILIN and LEGUMIN (LEG) are synthesized from several genes including LEGA, LEGB, LEGJ and CVC (CONVICILIN). The current hypothesis is that the plant circadian core clock genes are conserved in a wide array of species and that primary metabolism is to a large extent controlled by the plant circadian clock. Our aim was to investigate a possible link between gene expression of storage proteins and the circadian clock. We identified cowpea orthologues of the core clock genes VunLHY, VunTOC1, VunGI and VunELF3, the protein storage genes VunLEG, VunLEGJ, and VunCVC as well as nine candidate reference genes used in RT-PCR. ELONGATION FACTOR 1-A (ELF1A) resulted the most suitable reference gene. The clock genes VunELF3, VunGI, VunTOC1 and VunLHY showed a rhythmic expression profile in leaves with a typical evening/night and morning/midday phased expression. The diel patterns were not completely robust and only VungGI and VungELF3 retained a rhythmic pattern under free running conditions of darkness. Under field conditions, rhythmicity and phasing apparently faded during early pod and seed development and was regained in ripening pods for VunTOC1 and VunLHY. Mature seeds showed a rhythmic expression of VunGI resembling leaf tissue under controlled growth chamber conditions. Comparing time windows during developmental stages we found that VunCVC and VunLEG were significantly down regulated during the night in mature pods as compared to intermediate ripe pods, while changes in seeds were non-significant due to high variance. The rhythmic expression under field conditions was lost under growth chamber conditions. The core clock gene network is conserved in cowpea leaves showing a robust diel expression pattern except VunELF3 under growth chamber conditions. There appears to be a clock transcriptional reprogramming in pods and seeds compared to leaves. Storage protein deposition may be circadian regulated under field conditions but the strong environmental signals are not met under artificial growth conditions. Diel expression pattern in field conditions may result in better usage of energy for protein storage.
Katayama, K; Kobayashi, T; Oikawa, H; Honma, M; Ichihara, A
1998-05-19
In cell-free extracts of Alternaria solani, an enzymatic activity converting prosolanapyrone II to solanapyrones A and D via oxidation and subsequent Diels-Alder reaction has been found. Chromatography with DEAE-Sepharose provided two active fractions, pools 1 and 2. The former fraction converted prosolanapyrone II to solanapyrones A and D in a ratio of 2.2:1 with optical purities of 99% and 45% ee, respectively. The latter fraction did so in a ratio of 7.6:1 with 99% and nearly 0% ee, respectively. The enzyme partially purified from pool 2 native molecular weight of 40-62 kD and a pl of 4.25. The high reactivity of prosolanapyrone III in aqueous solution and the chromatographic behavior of the enzyme in pool 2 suggest that a single enzyme catalyzes both the oxidation and Diels-Alder reaction.
Diurnal patterns of methane flux from a seasonal wetland: mechanisms and methodology
Bansal, Sheel; Tangen, Brian; Finocchiaro, Raymond
2018-01-01
Methane emissions from wetlands are temporally dynamic. Few chamber-based studies have explored diurnal variation in methane flux with high temporal replication. Using an automated sampling system, we measured methane flux every 2.5 to 4 h for 205 diel cycles during three growing seasons (2013–2015) from a seasonal wetland in the Prairie Pothole Region of North America. During ponded conditions, fluxes were generally positive (i.e., methanogenesis dominant, 10.1 ± 0.8 mg m−2 h−1), had extreme range of variation (from −1 to 70 mg m−2 h−1), and were highest during late day. In contrast, during dry conditions fluxes were very low and primarily negative (i.e., oxidation dominant, −0.05 ± 0.002 mg m−2 h−1), with the highest (least negative) fluxes occurring at pre-dawn. During semi-saturated conditions, methane fluxes also were very low, oscillated between positive and negative values (i.e., balanced between methanogenesis and methane oxidation), and exhibited no diel pattern. Methane flux was positively correlated with air temperature during ponded conditions (r = 0.57) and negatively during dry conditions (r = −0.42). Multiple regression analyses showed that temperature, light and water-filled pore space explained 72% of variation in methane flux. Methane fluxes are highly temporally dynamic and follow contrasting diel patterns that are dependent on dominant microbial processes influenced by saturation state.
Seasonal and diel movements of white sturgeon in the lower columbia river
Parsley, M.J.; Popoff, N.D.; Van Der Leeuw, B. K.; Wright, C.D.
2008-01-01
Continuous monitoring of the movements and depths used by white sturgeon Acipenser transmontanus with acoustic telemetry technologies in the lower Columbia River provided information on diel and seasonal migrations, local movements, and site fidelity. White sturgeon moved to shallower water at night and showed greater activity, inferred from rates of movement, than during daytime. The extent of local movement within a season was variable among fish; some fish readily moved among habitats while the movements of others were more constrained. White sturgeon were absent from the study area (river kilometers 45-52) during winter and returned from upstream during the spring, confirming an upstream seasonal migration in the fall and downstream migration in spring. The return of individual fish and reoccupation of areas previously inhabited showed that some white sturgeon exhibit site fidelity. This work shows that studies seeking to characterize habitat for white sturgeon need to be cognizant of diel migrations and site fidelity. We urge caution in the use of limited fish location data to describe habitats if diel activities and fine-scale movements are not known.
Bénard, Camille; Bernillon, Stéphane; Biais, Benoît; Osorio, Sonia; Maucourt, Mickaël; Ballias, Patricia; Deborde, Catherine; Colombié, Sophie; Cabasson, Cécile; Jacob, Daniel; Vercambre, Gilles; Gautier, Hélène; Rolin, Dominique; Génard, Michel; Fernie, Alisdair R.; Gibon, Yves; Moing, Annick
2015-01-01
A detailed study of the diurnal compositional changes was performed in tomato (Solanum lycopersicum cv. Moneymaker) leaves and fruits. Plants were cultivated in a commercial greenhouse under two growth conditions: control and shaded. Expanding fruits and the closest mature leaves were harvested during two different day/night cycles (cloudy or sunny day). High-throughput robotized biochemical phenotyping of major compounds, as well as proton nuclear magnetic resonance and mass spectrometry metabolomic profiling, were used to measure the contents of about 70 metabolites in the leaves and 60 metabolites in the fruits, in parallel with ecophysiological measurements. Metabolite data were processed using multivariate, univariate, or clustering analyses and correlation networks. The shaded carbon-limited plants adjusted their leaf area, decreased their sink carbon demand and showed subtle compositional modifications. For source leaves, several metabolites varied along a diel cycle, including those directly linked to photosynthesis and photorespiration. These metabolites peaked at midday in both conditions and diel cycles as expected. However, transitory carbon storage was limited in tomato leaves. In fruits, fewer metabolites showed diel fluctuations, which were also of lower amplitude. Several organic acids were among the fluctuating metabolites. Diel patterns observed in leaves and especially in fruits differed between the cloudy and sunny days, and between the two conditions. Relationships between compositional changes in leaves and fruits are in agreement with the fact that several metabolic processes of the fruit appeared linked to its momentary supply of sucrose. PMID:25873655
Fadel, Salah; Hajbi, Youssef; Khouili, Mostafa; Lazar, Said; Suzenet, Franck; Guillaumet, Gérald
2014-01-01
Substituted 3,4-dihydro-1,8-naphthyridin-2(1H)-ones have been synthesized with the inverse electron-demand Diels-Alder reaction from 1,2,4-triazines bearing an acylamino group with a terminal alkyne side chain. Alkynes were first subjected to the Sonogashira cross-coupling reaction with aryl halides, the product of which then underwent an intramolecular inverse electron-demand Diels-Alder reaction to yield 5-aryl-3,4-dihydro-1,8-naphthyridin-2(1H)-ones by an efficient synthetic route.
High Activity and Efficient Turnover by a Simple, Self-Assembled "Artificial Diels-Alderase".
Martí-Centelles, Vicente; Lawrence, Andrew L; Lusby, Paul J
2018-02-28
The Diels-Alder (DA) reaction is a cornerstone of synthesis, yet Nature does not use catalysts for intermolecular [4+2] cycloadditions. Attempts to create artificial "Diels-Alderases" have also met with limited success, plagued by product inhibition. Using a simple Pd 2 L 4 capsule we now show DA catalysis that combines efficient turnover alongside enzyme-like hallmarks. This includes excellent activity (k cat /k uncat > 10 3 ), selective transition-state stabilization comparable to the most proficient DA catalytic antibodies, and control over regio- and chemoselectivity that would otherwise be difficult to achieve using small-molecule catalysts. Unlike other catalytic approaches that use synthetic capsules, this method is not defined by entropic effects; instead multiple H-bonding interactions modulate reactivity, reminiscent of enzymatic action.
Hirano, S S; Upper, C D
1989-03-01
The extent to which diel changes in the physical environment affect changes in population size and ice nucleation activity of Pseudomonas syringae on snap bean leaflets was determined under field conditions. To estimate bacterial population size and ice nucleation activity, bean leaflets were harvested at 2-h intervals during each of three 26-h periods. A tube nucleation test was used to assay individual leaflets for ice nuclei. Population sizes of P. syringae were determined by dilution plating of leaflet homogenates. The overall diel changes in P. syringae population sizes differed during each of the 26-h periods. In one 26-h period, there was a continuous increase in the logarithm of P. syringae population size despite intense solar radiation, absence of free moisture on leaf surfaces, and low relative humidity during the day. A mean doubling time of approximately 4.9 h was estimated for the 28-fold increase in P. syringae population size that occurred from 0900 to 0900 h during the 26-h period. However, doubling times of 3.3 and 1.9 h occurred briefly during this period from 1700 to 2300 h and from 0100 to 0700 h, respectively. Thus, growth rates of P. syringae in association with leaves in the field were of the same order of magnitude as optimal rates measured in the laboratory. The frequency with which leaflets bore ice nuclei active at -2.0, -2.2, and -2.5 degrees C varied greatly within each 26-h period. These large diel changes were inversely correlated primarily with the diel changes in air temperature and reflected changes in nucleation frequency rather than changes in population size of P. syringae. Thus, the response of bacterial ice nucleation activity to the physical environment was distinct from the changes in population size of ice nucleation-active P. syringae.
Temporal and spatial transcriptomic and microRNA dynamics of CAM photosynthesis in pineapple.
Wai, Ching M; VanBuren, Robert; Zhang, Jisen; Huang, Lixian; Miao, Wenjing; Edger, Patrick P; Yim, Won C; Priest, Henry D; Meyers, Blake C; Mockler, Todd; Smith, J Andrew C; Cushman, John C; Ming, Ray
2017-10-01
The altered carbon assimilation pathway of crassulacean acid metabolism (CAM) photosynthesis results in an up to 80% higher water-use efficiency than C 3 photosynthesis in plants making it a potentially useful pathway for engineering crop plants with improved drought tolerance. Here we surveyed detailed temporal (diel time course) and spatial (across a leaf gradient) gene and microRNA (miRNA) expression patterns in the obligate CAM plant pineapple [Ananas comosus (L.) Merr.]. The high-resolution transcriptome atlas allowed us to distinguish between CAM-related and non-CAM gene copies. A differential gene co-expression network across green and white leaf diel datasets identified genes with circadian oscillation, CAM-related functions, and source-sink relations. Gene co-expression clusters containing CAM pathway genes are enriched with clock-associated cis-elements, suggesting circadian regulation of CAM. About 20% of pineapple microRNAs have diel expression patterns, with several that target key CAM-related genes. Expression and physiology data provide a model for CAM-specific carbohydrate flux and long-distance hexose transport. Together these resources provide a list of candidate genes for targeted engineering of CAM into C 3 photosynthesis crop species. © 2017 The Authors The Plant Journal © 2017 John Wiley & Sons Ltd.
Drew, Gary S.; Bissonette, John A.
1997-01-01
Despite their temperate to subarctic geographic range, American martens (Martes americana) possess a thermally inefficient morphology. The lack of morphological adaptations for reducing thermal costs suggests that marten may use behavioral strategies to optimize thermal budgets. During the winters of 1989–1990 and 1990–1991, we radio-collared and monitored the diel activity of 7 martens. A log-linear model suggested that the presence or absence of light was the only factor associated with marten activity patterns (p < 0.001). A regression of the percentage of active fixes on ambient temperature failed to detect an association (b = −4.45, p = 0.084, n = 12). Contents of marten scats suggested that their activity was consistent with the prey-vulnerability hypothesis. While martens must balance multiple life requisites, their activity patterns suggest that they accept increased thermal costs in order to increase foraging efficiency. However, the nocturnal activity of martens during winter was also consistent with the hypothesis that they may be able to limit their own exposure to predation risk. The nocturnal habits of Newfoundland martens in the winter were consistent with the hypothesis of avoidance of predation risk.
NASA Astrophysics Data System (ADS)
Frank, K. L.; Rogers, K. L.; Wheat, C. G.; Alegado, R.
2016-12-01
Microbes play crucial roles in mediating biogeochemical cycling in coastal marine habitats. In shallow coastal ecosystems, excess primary productivity and respiration of pelagic phototrophic organisms generate striking diel variations in dissolved oxygen concentrations, leading to substantial vertical migration of redox transition zones in the sediment. However, the relationship between microbial community dynamics and the establishment of these geochemical gradients, especially over a diel time frame, remains poorly constrained. Here we examine the biogeochemical drivers of diel redox dynamics by integrating comprehensive geochemical, taxonomic, functional gene abundance, and thermodynamic datasets from Héeia Fishpond (HFP) sediment cores. HFP, an 88-acre tidally-influenced, shallow Hawaiian coastal estuarine system, is analogous to a large mesocosm embedded in a natural coastal environment, making it an ideal site for coastal biogeochemical studies. Taxonomic assessments of bacterial diversity via 16S rRNA genes revealed centimeter- scale variability with depth, with similar taxa present in all samples, but their relative abundances varied substantially among horizons. There were significant correlation between changes in geochemical composition and changes in community structure. Additionally, functional gene abundance was correlated with energy potential and aligned with activity. The taxanomic data and porewater geochemistry from HFP sediments suggest that redox variations observed in iron and sulfur speciation result from depth-related changes in microbial activity and community structure over a diel period. By linking community diversity to metabolic activity in the context of the geochemical environment, this research provides valuable insight into the connectivity of iron and sulfur metabolic modes.
Zydlewski, Joseph D.; Gorsky, Dimitry; Balsey, David
2016-01-01
Seasonal and daily vertical activity of lake whitefish Coregonus clupeaformis was studied in Clear Lake, Maine (253 ha), using acoustic telemetry from November 2004 to June 2009. Twenty adult lake whitefish were tagged with acoustic tags that had either a depth sensor or both depth and temperature sensors to assess vertical habitat use at a seasonal and daily resolution. Vertical habitat selection varied seasonally and was strongly influenced by temperature. Between December and April, when the lake was covered with ice, surface temperature was below 2°C and tagged individuals occupied deep areas of the lake (∼15 m). After ice-out, fish ascended into shallow waters (∼5 m), responding to increased water temperature and possibly to greater foraging opportunity. When surface water temperatures exceeded 20°C, fish descended below the developing thermocline (∼9 m), where they remained until surface temperatures fell below 20°C; fish then ascended into shallower depths, presumably for feeding and spawning. Through the winter, fish remained in thermal habitats that were warmer than the surface temperatures; in the summer, they selected depths with thermal habitats below 15°C. Though the amplitude varied greatly across seasons, lake whitefish displayed a strong diurnal pattern of activity as measured by vertical velocities. Fish were twofold more active during spring, summer, and fall than during winter. Lake whitefish exhibited diel vertical migrations, rising in the water column during nighttime and occupying deeper waters during the day. This pattern was more pronounced in the spring and fall and far less prominent during winter and summer. The strong linkage between temperature and habitat use may limit the current range of lake whitefish and may be directly impacted by climatic change.
Wang, Zhitao; Akamatsu, Tomonari; Wang, Kexiong; Wang, Ding
2014-01-01
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.
Wang, Zhitao; Akamatsu, Tomonari; Wang, Kexiong; Wang, Ding
2014-01-01
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. PMID:24823945
Hewson, Ian; Moisander, Pia H; Morrison, Amanda E; Zehr, Jonathan P
2007-05-01
We investigated diazotrophic bacterioplankton assemblage composition in the Heron Reef lagoon (Great Barrier Reef, Australia) using culture-independent techniques targeting the nifH fragment of the nitrogenase gene. Seawater was collected at 3 h intervals over a period of 72 h (i.e. over diel as well as tidal cycles). An incubation experiment was also conducted to assess the impact of phosphate (PO(4)3*) availability on nifH expression patterns. DNA-based nifH libraries contained primarily sequences that were most similar to nifH from sediment, microbial mat and surface-associated microorganisms, with a few sequences that clustered with typical open ocean phylotypes. In contrast to genomic DNA sequences, libraries prepared from gene transcripts (mRNA amplified by reverse transcription-polymerase chain reaction) were entirely cyanobacterial and contained phylotypes similar to those observed in open ocean plankton. The abundance of Trichodesmium and two uncultured cyanobacterial phylotypes from previous studies (group A and group B) were studied by quantitative-polymerase chain reaction in the lagoon samples. These were detected as transcripts, but were not detected in genomic DNA. The gene transcript abundance of these phylotypes demonstrated variability over several diel cycles. The PO(4)3* enrichment experiment had a clearer pattern of gene expression over diel cycles than the lagoon sampling, however PO(4)3* additions did not result in enhanced transcript abundance relative to control incubations. The results suggest that a number of diazotrophs in bacterioplankton of the reef lagoon may originate from sediment, coral or beachrock surfaces, sloughing into plankton with the flooding tide. The presence of typical open ocean phylotype transcripts in lagoon bacterioplankton may indicate that they are an important component of the N cycle of the coral reef.
Spatial and Temporal Dynamics of Carbon Fluxes in Glacial Meltwater Streams, Antarctica
NASA Astrophysics Data System (ADS)
Torrens, C.; Lyons, W. B.; McKnight, D. M.; Welch, K. A.; Gooseff, M. N.
2017-12-01
In the McMurdo Dry Valleys [MDV], Antarctica, glacial meltwater streams are the primary biogeochemical connectors linking glaciers, soils and lakes. These streams control the supply of nutrients and carbon to their terminal lakes, yet little is known about the magnitude, timing or distribution of these fluxes. The McMurdo Long Term Ecological Research project [MCM LTER] has collected over 20 years of sample data on dissolved organic and inorganic carbon in Taylor Valley streamwater; this is the first spatial and temporal analysis of this data. MDV streams are characterized by strong diel pulses in streamflow, specific electrical conductance, and temperature. Unlike temperate stream systems, there is no terrestrial vegetation, lateral overland flow or deep groundwater connection in MDV streams. As a result, the organic carbon is autochthonous, originating from stream microbial mats. Inorganic carbon is primarily bicarbonate; its source is hyporheic zone weathering. The carbonate system is in atmospheric equilibrium, reflecting the wide and shallow stream channels. Preliminary data show that the DOC flux varies with streamflow and is greater on the rising limb of the diel flow pulse. This pattern is more distinct in longer streams. DIC data does not show the same pattern, although the response may be blurred by a lag in hyporheic response to flood pulses and the lack of time-series data for alkalinity. Stream flood pulse dynamics control carbon loading to MDV lakes. As the climate changes, so will the timing and magnitude of diel flood pulses. This is likely to increase carbon loading to the Dry Valley lakes, altering the ecosystem carbon balance. This study increases our understanding of past and current patterns of carbon fluxes from streams to lakes; understanding past patterns will improve predictions of future changes.
NASA Astrophysics Data System (ADS)
Ivory, J.; Steinberg, D. K.; Latour, R. J.
2016-02-01
Temporal changes in mesozooplankton community structure affect planktonic food web interactions and biogeochemical cycling. Epipelagic mesozooplankton biomass in the Sargasso Sea has increased over the last two decades, with a related increase in zooplankton-mediated carbon export. Unknown, however, is what are the patterns and variability at different temporal scales (diel, seasonal, and interannual) in abundance of each major zooplankton taxon, and how do these patterns relate to physical and other environmental changes? We enumerated major taxa of mesozooplankton collected from monthly day and night net tows in the epipelagic zone at the Bermuda Atlantic Time-series Study (BATS) site in the Sargasso Sea from 1999 to 2010. Abundances of each taxon were determined using a ZooScan optical imaging system and microscopy. Generalized Linear Models (GLMs) were used to determine what environmental parameters best explain abundance of major taxa. We used annual averages to consider broader patterns. Zooplankton taxa with the most pronounced diel vertical migration (i.e., night:day ratio, N:D, >>1) included Limacina spp. pteropods (N:D=2.02), euphausiids (1.93), calanoid copepods (1.34), and heteropods (1.34). Taxa with a pronounced spring abundance peak included chaetognaths, larvaceans, and Limacina spp. pteropods, while harpacticoid copepods peaked in late summer, and calanoid copepods in both spring and summer. Environmental variables affecting abundance differed amongst taxa. For example, calanoid copepod density was highly influenced by the abundance of a major predator- chaetognaths. Multi-year densities of calanoid copepods and ostracods both increased with increasing Water Column Stratification Index and the Atlantic Multidecadal Oscillation (AMO) index, indicating warmer sea surface temperatures are favorable for these taxa. We discuss how these temporal patterns at different scales help predict effects of global climate change on the zooplankton community.
Eyes Wide Shut: the impact of dim-light vision on neural investment in marine teleosts.
Iglesias, Teresa L; Dornburg, Alex; Warren, Dan L; Wainwright, Peter C; Schmitz, Lars; Economo, Evan P
2018-05-28
Understanding how organismal design evolves in response to environmental challenges is a central goal of evolutionary biology. In particular, assessing the extent to which environmental requirements drive general design features among distantly related groups is a major research question. The visual system is a critical sensory apparatus that evolves in response to changing light regimes. In vertebrates, the optic tectum is the primary visual processing centre of the brain and yet it is unclear how or whether this structure evolves while lineages adapt to changes in photic environment. On one hand, dim-light adaptation is associated with larger eyes and enhanced light-gathering power that could require larger information processing capacity. On the other hand, dim-light vision may evolve to maximize light sensitivity at the cost of acuity and colour sensitivity, which could require less processing power. Here, we use X-ray microtomography and phylogenetic comparative methods to examine the relationships between diel activity pattern, optic morphology, trophic guild and investment in the optic tectum across the largest radiation of vertebrates-teleost fishes. We find that despite driving the evolution of larger eyes, enhancement of the capacity for dim-light vision generally is accompanied by a decrease in investment in the optic tectum. These findings underscore the importance of considering diel activity patterns in comparative studies and demonstrate how vision plays a role in brain evolution, illuminating common design principles of the vertebrate visual system. © 2018 European Society For Evolutionary Biology. Journal of Evolutionary Biology © 2018 European Society For Evolutionary Biology.
Examining diel patterns of soil and xylem moisture using electrical resistivity imaging
NASA Astrophysics Data System (ADS)
Mares, Rachel; Barnard, Holly R.; Mao, Deqiang; Revil, André; Singha, Kamini
2016-05-01
The feedbacks among forest transpiration, soil moisture, and subsurface flowpaths are poorly understood. We investigate how soil moisture is affected by daily transpiration using time-lapse electrical resistivity imaging (ERI) on a highly instrumented ponderosa pine and the surrounding soil throughout the growing season. By comparing sap flow measurements to the ERI data, we find that periods of high sap flow within the diel cycle are aligned with decreases in ground electrical conductivity and soil moisture due to drying of the soil during moisture uptake. As sap flow decreases during the night, the ground conductivity increases as the soil moisture is replenished. The mean and variance of the ground conductivity decreases into the summer dry season, indicating drier soil and smaller diel fluctuations in soil moisture as the summer progresses. Sap flow did not significantly decrease through the summer suggesting use of a water source deeper than 60 cm to maintain transpiration during times of shallow soil moisture depletion. ERI captured spatiotemporal variability of soil moisture on daily and seasonal timescales. ERI data on the tree showed a diel cycle of conductivity, interpreted as changes in water content due to transpiration, but changes in sap flow throughout the season could not be interpreted from ERI inversions alone due to daily temperature changes.
NASA Astrophysics Data System (ADS)
Grantz, D. A.; Vu, H.; Heath, R. L.; Burkey, K.
2011-12-01
Ozone (O3) injury to vegetation can be conceptually divided into three stages: 1) O3 entrance into the leaf including fractionation of stomatal vs. non-stomatal deposition; 2) O3 overcoming initial metabolic defenses within individual leaves, and 3) oxidant attack by O3 or derivatives on bioreceptors to produce injury. Ozone deposition at canopy scale and uptake at leaf scale are routinely obtained by observational and modeling techniques (Massman and Grantz, 1995). Injury can be assessed experimentally. However, predictive association between ozone concentration or flux and injury is currently not well characterized. This is due to uncertainties in rates and capacities of ozone detoxification, the nature of plant defense mechanisms, and their temporal (diel and seasonal) variability (Heath et al., 2009; Massman et al., 2000). We have developed a plant sensitivity parameter (SO3) relating injury (I) to the sum of O3 flux and photon flux density (FO3 + PPFD) during exposure. By restricting leaf exposure to O3 to a brief (15 min) pulse, we assess passive defense mechanisms, assuming that the pulse duration provides insufficient time for induction of additional (active) defense capacity during exposure. Greenhouse grown Pima cotton was exposed in chambers to pulsed O3 at a range of concentrations, stomatal conductance was measured directly pre- and post-exposure, and injury was assessed 1 week later using several indicators. SO3, determined at 2 hour intervals, exhibited clear diel trends, with maximal sensitivity shortly after solar noon, and minimal sensitivity early and late in the photoperiod. This diel pattern of SO3 did not support suggestions that plant defense is correlated with instantaneous photosynthetic rate. There was only weak correlation between SO3 and whole leaf ascorbate, ascorbate redox poise, or total antioxidant capacity, though future measurements of apoplastic antioxidants may improve these relationships. The parameter, SO3, may be directly related to the weighting factor commonly used as a surrogate for plant defense in model relationships between injury and O3 flux (e.g. Massman et al. 2000). Diurnally varying SO3 incorporates the combined oxidative stresses of O3 and photochemistry, and can be combined with natural diel cycles of ozone concentration and models of stomatal conductance and photosynthesis, to yield integrated impacts of O3 on injury to vegetation.
Enzymatic catalysis of the Diels-Alder reaction in the biosynthesis of natural products.
Oikawa, Hideaki; Tokiwano, Tetsuo
2004-06-01
Recent studies on enzymes catalyzing the Diels- Alder reaction. often named "Diels-Alderases", clearlydemonstrated the involvement of this synthetically useful reaction in the biosynthesis of natural products.This review covers natural Diels-Alder type cycloadducts. synthetic efforts on the chemical feasibility ofthe biosynthctic Diels - Alder reaction and a brief history of studies on Diels-Alderases. In addition,reaction mechanisms of artificial and natural Diels--Alderases are discussed.
de Jong, Margje E.; Komdeur, Jan; Pschernig, Elisabeth; Loonen, Maarten J. J. E.; Millesi, Eva; Weiß, Brigitte M.
2017-01-01
Here we describe the excretion pattern of corticosterone metabolites collected from droppings in barnacle goslings (Branta leucopsis) raised under 24 hours of continuous natural light in the Arctic. In lower latitudes, circulating corticosterone peaks around waking and shows a nadir between midnight and 4:00, whereas the peak and nadir are time-delayed slightly when measuring corticosterone metabolites from droppings. Photoperiod, along with other environmental factors, helps to entrain an animal’s endogenous rhythm to that of the natural world. North of the Arctic Circle, photoperiod may not be a reliable cue as light is continuously absent during the winter and continuously present during the summer. Here, for the first time, we used droppings to describe a 24-hour excretion pattern of corticosterone metabolites (CORTm). By applying circular statistics for dependent data, we found a diel rhythmic pattern even under continuous natural light. We discuss potential alternative ‘Zeitgeber’ that may function even in the polar regions, focusing on melatonin. We propose a line of research to measure melatonin non-invasively from droppings. We also provide a validation of the adopted enzyme immunoassay (EIA) that was originally developed for greylag geese. PMID:28787012
Diel-scale temporal dynamics recorded for bacterial groups in Namib Desert soil
Gunnigle, Eoin; Frossard, Aline; Ramond, Jean-Baptiste; Guerrero, Leandro; Seely, Mary; Cowan, Don A.
2017-01-01
Microbes in hot desert soil partake in core ecosystem processes e.g., biogeochemical cycling of carbon. Nevertheless, there is still a fundamental lack of insights regarding short-term (i.e., over a 24-hour [diel] cycle) microbial responses to highly fluctuating microenvironmental parameters like temperature and humidity. To address this, we employed T-RFLP fingerprinting and 454 pyrosequencing of 16S rRNA-derived cDNA to characterize potentially active bacteria in Namib Desert soil over multiple diel cycles. Strikingly, we found that significant shifts in active bacterial groups could occur over a single 24-hour period. For instance, members of the predominant Actinobacteria phyla exhibited a significant reduction in relative activity from morning to night, whereas many Proteobacterial groups displayed an opposite trend. Contrary to our leading hypothesis, environmental parameters could only account for 10.5% of the recorded total variation. Potential biotic associations shown through co-occurrence networks indicated that non-random inter- and intra-phyla associations were ‘time-of-day-dependent’ which may constitute a key feature of this system. Notably, many cyanobacterial groups were positioned outside and/or between highly interconnected bacterial associations (modules); possibly acting as inter-module ‘hubs’ orchestrating interactions between important functional consortia. Overall, these results provide empirical evidence that bacterial communities in hot desert soils exhibit complex and diel-dependent inter-community associations. PMID:28071697
Diel-scale temporal dynamics recorded for bacterial groups in Namib Desert soil
NASA Astrophysics Data System (ADS)
Gunnigle, Eoin; Frossard, Aline; Ramond, Jean-Baptiste; Guerrero, Leandro; Seely, Mary; Cowan, Don A.
2017-01-01
Microbes in hot desert soil partake in core ecosystem processes e.g., biogeochemical cycling of carbon. Nevertheless, there is still a fundamental lack of insights regarding short-term (i.e., over a 24-hour [diel] cycle) microbial responses to highly fluctuating microenvironmental parameters like temperature and humidity. To address this, we employed T-RFLP fingerprinting and 454 pyrosequencing of 16S rRNA-derived cDNA to characterize potentially active bacteria in Namib Desert soil over multiple diel cycles. Strikingly, we found that significant shifts in active bacterial groups could occur over a single 24-hour period. For instance, members of the predominant Actinobacteria phyla exhibited a significant reduction in relative activity from morning to night, whereas many Proteobacterial groups displayed an opposite trend. Contrary to our leading hypothesis, environmental parameters could only account for 10.5% of the recorded total variation. Potential biotic associations shown through co-occurrence networks indicated that non-random inter- and intra-phyla associations were ‘time-of-day-dependent’ which may constitute a key feature of this system. Notably, many cyanobacterial groups were positioned outside and/or between highly interconnected bacterial associations (modules); possibly acting as inter-module ‘hubs’ orchestrating interactions between important functional consortia. Overall, these results provide empirical evidence that bacterial communities in hot desert soils exhibit complex and diel-dependent inter-community associations.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kraus, G.A.; Li, J.; Gordon, M.S.
1993-06-30
The quinone subunit is contained in a broad range of biologically important natural products such as frenolicin B, which is a member of the pyranonaphthoquinone family. The diverse biological activity of quinones has led to the development of several new synthetic methods for quinones. Among the pathways featuring a cycloaddition reaction, one of the most general methods for the regiospecific synthesis of substituted quinones was pioneered by H.J. Rapoport and others. This method involves the Diels-Alder reaction of a substituted quinone. As part of a program to evaluate the directing effects of functional groups not directly attached to the atomsmore » undergoing Diels-Alder cycloaddition, we now report that remote substituents on a dienophile can confer excellent regioselectivity in Diels-Alder reactions. This work has led to an extremely direct synthesis of the pyranonaphthoquinone framework and to the first synthesis of frenolicin B (1). 19 refs., 1 fig.« less
[Chemistry and biosynthesis of prenylflavonoids].
Nomura, T
2001-07-01
Many isoprenylated flavonoids have been isolated from mulberry trees and related plants (Moraceae). Among them, kuwanons G (13) and H (14) were the first isolated active substances exhibiting a hypotensive effect from the Japanese Morus root bark. These compounds are considered to be formed through an enzymatic Diels-Alder reaction of a chalcone (15) and dehydro-kuwanon C (16) or its equivalent. Since that time, about forty kinds of Diels-Alder type adducts structurally similar to that of 13 have been isolated from the moraceous plants. Some strains of Morus alba as well as M. bombycis callus tissues have a high productivity of mulberry Diels-Alder type adducts, such as chalcomoracin (26) and kuwanon J (28). The biosynthesis of the mulberry Diels-Alder type adducts has been studied with the aid of the cell strain. Chalcomoracin (26) and kuwanon J (28) were proved to be enzymatic Diels-Alder type reaction products by the administration experiment with O-methylchalcone derivatives. Furthermore, for the isoprenoid biosynthesis of prenylflavonoids in Morus alba callus tissues, a novel way through the junction of glycolysis and pentose-phosphate cycle was proposed. The crude enzyme fraction catalyzing the Morus Diels-Alder type reaction could be isolated. Studies of phenolic constituents of licorice (Glycyrrhiza species) were carried out. On the course of the structure determination of the phenolic constituents of licorice, two new NMR structure determination methods for prenylflavonoids were found. Furthermore, the prenylphenols isolated from licorice were summarized according to the origin of the materials.
Chemistry and biosynthesis of isoprenylated flavonoids from Japanese mulberry tree
Nomura, Taro; Hano, Yoshio; Fukai, Toshio
2009-01-01
Many isoprenylated flavonoids have been isolated from Japanese mulberry tree (Moraceae). Among them, kuwanons G (1) and H (2) were the first isolated active substances exhibiting a hypotensive effect. These compounds are considered to be formed through an enzymatic Diels-Alder type reaction between an isoprenyl portion of an isoprenylphenol as the diene and an α, β-double bond of chalcone as the dienophile. The absolute configurations of these Diels-Alder type adducts were confirmed by three different methods. The stereochemistries of the adducts were consistent with those of ones in the Diels-Alder reaction involving exo- and endo-addition. Some strains of Morus alba callus tissues have a high productivity of mulberry Diels-Alder type adducts, such as chalcomoracin (3) and kuwanon J (4). The biosynthetic studies of the mulberry Diels-Alder type adducts have been carried out with the aid of the cell strain. Chalcomoracin (3) and kuwanon J (4) were proved to be enzymatic Diels-Alder type reaction products by the administration experiments with O-methylchalcone derivatives. Furthermore, for the isoprenoid biosynthesis of prenylflavonoids in Morus alba callus tissues by administration of [1,3-13C2]- and [2-13C]-glycerol, a novel way through the junction of glycolysis and pentose-phosphate cycle was proved. Two independent isoprenoid biosynthetic pathways, that for sterols and that for isoprenoidphenols, operate in the Morus alba cell cultures. The former is susceptible to compactin (ML-236) and the latter resists to compactin in the cell cultures, respectively. PMID:19907125
Ng, Wai Ho Albert; Liu, Hongbin
2015-02-01
We investigated the relationship between daily growth rates and diel variation of carbon (C) metabolism and C to nitrogen (N) ratio under P- and N-limitation in the green algae Chlorella autotrophica. To do this, continuous cultures of C. autotrophica were maintained in a cyclostat culture system under 14:10 light:dark cycle over a series of P- and N-limited growth rates. Cell abundance, together with cell size, as reflected by side scatter signal from flow cytometric analysis demonstrated a synchronized diel pattern with cell division occurring at night. Under either type of nutrient limitation, the cellular C:N ratio increased through the light period and decreased through the dark period over all growth rates, indicating a higher diel variation of C metabolism than that of N. Daily average cellular C:N ratios were higher at lower dilution rates under both types of nutrient limitation but cell enlargement was only observed at lower dilution rates under P-limitation. Carbon specific growth rates during the dark period positively correlated with cellular daily growth rates (dilution rates), with net loss of C during night at the lowest growth rates under N-limitation. Under P-limitation, dark C specific growth rates were close to zero at low dilution rates but also exhibited an increasing trend at high dilution rates. In general, diel variations of cellular C:N were low when dark C specific growth rates were high. This result indicated that the fast growing cells performed dark C assimilation at high rates, hence diminished the uncoupling of C and N metabolism at night. © 2014 Phycological Society of America.
Diel changes in water chemistry in an arsenic-rich stream and treatment-pond system
Gammons, C.H.; Grant, T.M.; Nimick, D.A.; Parker, S.R.; DeGrandpre, M.D.
2007-01-01
Arsenic concentrations are elevated in surface waters of the Warm Springs Ponds Operable Unit (WSPOU), located at the head of the upper Clark Fork River Superfund site, Montana, USA. Arsenic is derived from historical deposition of smelter emissions (Mill and Willow Creeks) and historical mining and milling wastes (Silver Bow Creek). Although long-term monitoring has characterized the general seasonal and flow-related trends in As concentrations in these streams and the pond system used to treat Silver Bow Creek water, little is known about solubility controls and sorption processes that influence diel cycles in As concentrations. Diel (24-h) sampling was conducted in July 2004 and August 2005 at the outlet of the treatment ponds, at two locations along a nearby reconstructed stream channel that diverts tributary water around the ponds, and at Silver Bow Creek 2??km below the ponds. Dissolved As concentration increased up to 51% during the day at most of the stream sites, whereas little or no diel change was displayed at the treatment-pond outlet. The strong cycle in streams is explained by pH- and temperature-dependent sorption of As onto hydrous metal oxides or biofilms on the streambed. Concentrations of dissolved Ca2+ and HCO3- at the stream sites showed a diel temporal pattern opposite to that of As, and geochemical modeling supports the hypothesis that the concentrations of Ca2+ and HCO3- were controlled by precipitation of calcite during the warm afternoon hours when pH rose above 9.0. Nightly increases in dissolved Mn and Fe(II) concentrations were out of phase with concentrations of other divalent cations and are more likely explained by redox phenomena. ?? 2007 Elsevier B.V. All rights reserved.
Gadomski, D.M.; Barfoot, C.A.
1998-01-01
Diel and distributional abundance patterns of free embryos and larvae of fishes in the lower Columbia River Basin were investigated. Ichthyoplankton samples were collected in 1993 during day and night in the main-channel and a backwater of the lower Columbia River, and in a tributary, the Deschutes River. Fish embryos and larvae collected in the main-channel Columbia River were primarily (85.6%) of native taxa (peamouth Mylocheilus caurinus, northern squawfish Ptychocheilus oregonensis, suckers Catostomus spp., and sculpins Cottus spp.), with two introduced species (American shad Alosa sapidissima and common carp Cyprinus carpio) comprising a smaller percentage of the catch (13.3%). Similarly, in the Deschutes River native taxa [lampreys (Petromyzontidae), minnows (Cyprinidae), and suckers Catostomus spp.] dominated collections (99.5% of the catch). In contrast, 83.5% of embryos and larvae in the Columbia River backwater were of introduced taxa [American shad, common carp, and sunfishes (Centrarchidae)]. In all locations, all dominant taxa except sculpins were collected in significantly greater proportions at night. Taxon-specific differences in proportions of embryos and larvae collected at night can in some instances be related to life history styles. In the main-channel Columbia River, northern squawfish and peamouth were strongly nocturnal and high proportions still had yolksacs, suggesting that they had recently hatched and were drifting downriver to rearing areas. In contrast, sculpin abundances were similar during day and night, and sculpins mostly had depleted yolksacs, indicating sculpins were feeding and rearing in offshore limnetic habitats. Taxon-specific diel abundance patterns and their causes must be considered when designing effective sampling programs for fish embryos and larvae.
Vebrová, Lucie; van Nieuwenhuijzen, Andre; Kolář, Vojtěch; Boukal, David S
2018-06-19
Chironomids, a major invertebrate taxon in many standing freshwaters, rely on adult flight to reach new suitable sites, yet the impact of weather conditions on their flight activity is little understood. We investigated diel and seasonal flight activity patterns of aquatic and terrestrial chironomids in a reclaimed sandpit area and analysed how weather conditions and seasonality influenced their total abundance and species composition. Air temperature, relative humidity, wind speed, and air pressure significantly affected total flight activity of both groups, but not in the same way. We identified an intermediate temperature and humidity optimum for the flight activity of terrestrial chironomids, which contrasted with weaker, timescale-dependent relationships in aquatic species. Flight activity of both groups further declined with wind speed and increased with air pressure. Observed flight patterns also varied in time on both daily and seasonal scale. Flight activity of both groups peaked in the evenings after accounting for weather conditions but, surprisingly, aquatic and terrestrial chironomids used partly alternating time windows for dispersal during the season. This may be driven by different seasonal trends of key environmental variables in larval habitats and hence implies that species phenologies and conditions experienced by chironomid larvae (and probably other aquatic insects with short-lived adults) influence adult flight patterns more than weather conditions. Our results provide detailed insights into the drivers of chironomid flight activity and highlight the methodological challenges arising from the inherent collinearity of weather characteristics and their diurnal and seasonal cycles.
NASA Astrophysics Data System (ADS)
Christel, Isadora; Navarro, Joan; del Castillo, Marcos; Cama, Albert; Ferrer, Xavier
2012-01-01
A knowledge of the foraging strategies of marine predators is essential to understand the intrinsic factors controlling their distribution, abundance and their ecological function within the marine ecosystem. Here, we investigated for the first time the foraging movements and activity patterns of Audouin's gull Larus audouinii by using satellite-tracking data from eight breeding adults in the main colony of the species worldwide (Ebro Delta, NW Mediterranean). Tagged gulls foraged in the marine area close to the breeding colony (62% of foraging locations) and in the terrestrial area of the Ebro Delta (mainly rice fields; 38% of foraging locations). The foraging activity patterns changed significantly throughout the day; lower from dusk through the first half of the night (19-1 h; 32% of active locations) and higher during the rest of the day (1-19 h; 75.5 ± 4.3% of active locations). These results confirm the foraging plasticity of this seabird and, based on previous information about the dietary habits of this species, we hypothesize how its time-dependent activity patterns and habitat use could be associated with variations in the availability of marine food resources (e.g. diel vertical migrations of pelagic fish) and the exploitation of terrestrial resources (e.g. American crayfish Procambarus clarkii).
A dynamic optimization model of the diel vertical distribution of a pelagic planktivorous fish
NASA Astrophysics Data System (ADS)
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.
Balistrieri, Laurie S.; Nimick, David A.; Mebane, Christopher A.
2012-01-01
Evaluating water quality and the health of aquatic organisms is challenging in systems with systematic diel (24 hour) or less predictable runoff-induced changes in water composition. To advance our understanding of how to evaluate environmental health in these dynamic systems, field studies of diel cycling were conducted in two streams (Silver Bow Creek and High Ore Creek) affected by historical mining activities in southwestern Montana. A combination of sampling and modeling tools were used to assess the toxicity of metals in these systems. Diffusive Gradients in Thin Films (DGT) samplers were deployed at multiple time intervals during diel sampling to confirm that DGT integrates time-varying concentrations of dissolved metals. Thermodynamic speciation calculations using site specific water compositions, including time-integrated dissolved metal concentrations determined from DGT, and a competitive, multiple-metal biotic ligand model incorporated into the Windemere Humic Aqueous Model Version 6.0 (WHAM VI) were used to determine the chemical speciation of dissolved metals and biotic ligands. The model results were combined with previously collected toxicity data on cutthroat trout to derive a relationship that predicts the relative survivability of these fish at a given site. This integrative approach may prove useful for assessing water quality and toxicity of metals to aquatic organisms in dynamic systems and evaluating whether potential changes in environmental health of aquatic systems are due to anthropogenic activities or natural variability.
Origins of Stereoselectivity in the trans-Diels-Alder Paradigm
Paton, Robert S.; Mackey, Joel L.; Kim, Woo Han; Lee, Jun Hee; Danishefsky, Samuel J.; Houk, K. N.
2010-01-01
The regioselectivity and stereoselectivity aspects of the Diels-Alder/radical hydrodenitration reaction sequence leading to trans-fused ring systems have been investigated with density functional calculations. A continuum of transition structures representing Diels-Alder and hetero-Diels-Alder cycloadditions as well as a sigmatropic rearrangement have been located, and they all lie very close in energy on the potential energy surface. All three pathways are found to be important in the formation of the Diels-Alder adduct. Reported regioselectivities are reproduced by the calculations. The stereoselectivity of radical hydrodenitration of the cis-Diels-Alder adduct is found to be related to the relative conformational stabilities of bicyclic radical intermediates. Overall, the computations provide understanding of the regioselectivities and stereoselectivities of the trans-Diels-Alder paradigm. PMID:20557046
Seasonality of diel cycles of dissolved trace-metal concentrations in a Rocky Mountain stream
Nimick, D.A.; Cleasby, T.E.; McCleskey, R. Blaine
2005-01-01
Substantial diel (24-h) cycles in dissolved (0.1-??m filtration) metal concentrations were observed during summer low flow, winter low flow, and snowmelt runoff in Prickly Pear Creek, Montana. During seven diel sampling episodes lasting 34-61.5 h, dissolved Mn and Zn concentrations increased from afternoon minimum values to maximum values shortly after sunrise. Dissolved As concentrations exhibited the inverse timing. The magnitude of diel concentration increases varied in the range 17-152% for Mn and 70-500% for Zn. Diel increases of As concentrations (17-55%) were less variable. The timing of minimum and maximum values of diel streamflow cycles was inconsistent among sampling episodes and had little relation to the timing of metal concentration cycles, suggesting that geochemical rather than hydrological processes are the primary control of diel metal cycles. Diel cycles of dissolved metal concentrations should be assumed to occur at any time of year in any stream with dissolved metals and neutral to alkaline pH. ?? Springer-Verlag 2005.
Gordon H. Reeves; Jon B. Grunbaum; Dirk W. Lang
2009-01-01
The seasonal diel behaviour of age 1+ steelhead from Coast and Cascade Range streams in Oregon was examined in the field and in laboratory streams. During the summer, fish from both areas were active during the day in natural streams: they held position in the water column in moderate velocities and depths. At night, fish were in slower water, closer to the bottom...
Martín-Acosta, Pedro; Feresin, Gabriela; Tapia, Alejandro; Estévez-Braun, Ana
2016-10-21
A highly efficient and regioselective approach to new polycyclic embelin derivatives through a domino Knoevenagel condensation/intramolecular hetero Diels-Alder reaction using O-(arylpropynyloxy)-salicylaldehydes in the presence of ethylenediamine diacetate (EDDA) is reported. This organocatalyzed protocol is compatible toward a wide range of aryl-substituted alkynyl ethers with electron-donating and electron-withdrawing groups. When other active methylene compounds were subjected to this domino reaction the corresponding adducts were obtained in high yield.
Diels-Alder reactions of 12-hydroxy-9(10®20)-5aH-abeo-abieta-1(10),8(9),12(13)-triene-11,14-dione.
Majetich, George; Zhang, Yong; Tian, Xinrong; Zou, Ge; Li, Yang; Wang, Yangyang; Hu, Shougang; Huddleston, Eric
2013-06-14
12-Hydroxy-9(10-->20)-5aH-abeo-abieta-1(10),8(9),12(13)-triene-11,14-dione (quinone 2) served as the dienophile in numerous intermolecular Diels-Alder reactions. These cycloadditions were conducted either thermally (including microwave heating) or with Lewis acid activation. While most dienes reacted with quinone 2 in good chemical yield, others were incompatible under the experimental conditions used.
Covalently crosslinked diels-alder polymer networks.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bowman, Christopher; Adzima, Brian J.; Anderson, Benjamin John
2011-09-01
This project examines the utility of cycloaddition reactions for the synthesis of polymer networks. Cycloaddition reactions are desirable because they produce no unwanted side reactions or small molecules, allowing for the formation of high molecular weight species and glassy crosslinked networks. Both the Diels-Alder reaction and the copper-catalyzed azide-alkyne cycloaddition (CuAAC) were studied. Accomplishments include externally triggered healing of a thermoreversible covalent network via self-limited hysteresis heating, the creation of Diels-Alder based photoresists, and the successful photochemical catalysis of CuAAC as an alternative to the use of ascorbic acid for the generation of Cu(I) in click reactions. An analysis ofmore » the results reveals that these new methods offer the promise of efficiently creating robust, high molecular weight species and delicate three dimensional structures that incorporate chemical functionality in the patterned material. This work was performed under a Strategic Partnerships LDRD during FY10 and FY11 as part of a Sandia National Laboratories/University of Colorado-Boulder Excellence in Science and Engineering Fellowship awarded to Brian J. Adzima, a graduate student at UC-Boulder. Benjamin J. Anderson (Org. 1833) was the Sandia National Laboratories point-of-contact for this fellowship.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bodie, J.R.; Burke, V.J.; Smith, K.R.
1996-07-01
Diel nest temperature profiles were recorded form natural nests of eastern mud turtles (Kinosternon subrubrum) and Florida cooters (Pseudemys floridana) to determine whether nest microhabitat selection compensates for the effect of interspecific differences in nest depth on nest temperature. Kinosternon subrubrum nest depths were significantly shallower than those of P. floridana (t = 2.93, P < 0.01). We predicted that differences in nest depth would result in K. subrubrum nests being cooler at night and warmer during daylight than the deeper P. floridana nests. Diel temperature patterns agreed with out predictions at night, but P. floridana nest temperatures were notmore » lower than K. subrubrum nest temperatures during the day. Soil composition, slope and soil moisture were similar for the nest of both species. However, the amount of sunlight reaching the soil above K. subrubrum nest sites was substantially less than the amount above P. floridana nest sites. We suggest that these species select habitats for oviposition that differ in the amount and types of vegetative cover, which in turn affect exposure to sunlight and ultimately nest temperature. 27 refs., 2 figs.« less
Seasonal drift and feeding periodicity during summer of the amphipod, Gammarus psuedolimnaeus
Johnson, James H.
2014-01-01
Downstream drift of aquatic invertebrates is an important ecological process that varies temporally. Seasonal patterns of diel drift and diel feeding periodicity during summer of the amphipod Gammarus pseudolimnaeus were examined in a small stream in central New York. Seasonal trends in drift were similar with peak drift occurring from 2000 to 0400 h. Very little drift occurred during the day. Feeding intensity of G. pseudolimnaeus was greatest from 2000 to 0400 h and was significantly greater than at 0400 to 0800 h and 0800 to 1200 h. Previous research on feeding periodicity of this species found no evidence of periods of increased food consumption. Conflicting results between this study and earlier studies may be due to sampling drifting versus non-drifting amphipods.
Diel periodicity of drift of larval fishes in tributaries of Lake Ontario
Johnson, J. H.; McKenna, J.E.
2007-01-01
Diel patterns of downstream drift were examined during mid-June in three tributaries of Lake Ontario. Larval fishes were collected in drift nets that were set in each stream for 72 consecutive hours and emptied at 4-h intervals. Fantail darter (Ethostoma flabellare) and blacknose dace (Rhinichthys atractulus) were the two most abundant native stream fishes and were two of the three species collected in the ichthyoplankton drift. Fantail darter larvae comprised 100%, 98.9%, and 70.2% of the ichthyoplankton in the three streams. Most larval fishes (96%) drifted at night with peak catches occurring at 2400h in Orwell Brook and Trout Brook and 0400h in Little Sandy Creek. Based on stream temperatures, peak spawning and larval drift of blacknose dace probably occurred later in the season.
When should fig fruit produce volatiles? Pattern in a ripening process
NASA Astrophysics Data System (ADS)
Borges, Renee M.; Ranganathan, Yuvaraj; Krishnan, Anusha; Ghara, Mahua; Pramanik, Gautam
2011-11-01
Ripe fruit need to signal their presence to attract dispersal agents. Plants may employ visual and/or olfactory sensory channels to signal the presence of ripe fruit. Visual signals of ripe fruit have been extensively investigated. However, the volatile signatures of ripe fruit that use olfactorily-oriented dispersers have been scarcely investigated. Moreover, as in flowers, where floral scents are produced at times when pollinators are active (diurnal versus nocturnal), whether plants can modulate the olfactory signal to produce fruit odours when dispersers are active in the diel cycle is completely unknown. We investigated day-night differences in fruit odours in two species of figs, Ficus racemosa and Ficus benghalensis. The volatile bouquet of fruit of F. racemosa that are largely dispersed by bats and other mammals was dominated by fatty acid derivatives such as esters. In this species in which the ripe fig phase is very short, and where the figs drop off soon after ripening, there were no differences between day and night in fruit volatile signature. The volatile bouquet of fruit of F. benghalensis that has a long ripening period, however, and that remain attached to the tree for extended periods when ripe, showed an increase in fatty acid derivatives such as esters and of benzenoids such as benzaldehyde at night when they are dispersed by bats, and an elevation of sesquiterpenes during the day when they are dispersed by birds. For the first time we provide data that suggest that the volatile signal produced by fruit can show diel differences based on the activity period of the dispersal agent.
NASA Astrophysics Data System (ADS)
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.
Lee, Kang M; Driever, Steven M; Heuvelink, Ep; Rüger, Simon; Zimmermann, Ulrich; de Gelder, Arie; Marcelis, Leo F M
2012-12-01
Relative changes in cell turgor of leaves of well-watered tomato plants were evaluated using the leaf patch clamp pressure probe (LPCP) under dynamic greenhouse climate conditions. LPCP changes, a measure for relative changes in cell turgor, were monitored at three different heights of transpiring and non-transpiring leaves of tomato plants on sunny and cloudy days simultaneously with whole plant water uptake. Clear diel patterns were observed for relative changes of cell turgor of both transpiring and non-transpiring leaves, which were stronger on sunny days than on cloudy days. A clear effect of canopy height was also observed. Non-transpiring leaves showed relative changes in cell turgor that closely followed plant water uptake throughout the day. However, in the afternoon the relative changes of cell turgor of the transpiring leaves displayed a delayed response in comparison to plant water uptake. Subsequent recovery of cell turgor loss of transpiring leaves during the following night appeared insufficient, as the pre-dawn turgescent state similar to the previous night was not attained. Copyright © Physiologia Plantarum 2012.
Barnard, D R; Knue, G J; Dickerson, C Z; Bernier, U R; Kline, D L
2011-06-01
Capture rates of insectary-reared female Aedes albopictus (Skuse), Anopheles quadrimaculatus Say, Culex nigripalpus Theobald, Culex quinquefasciatus Say and Aedes triseriatus (Say) in CDC-type light traps (LT) supplemented with CO2 and using the human landing (HL) collection method were observed in matched-pair experiments in outdoor screened enclosures. Mosquito responses were compared on a catch-per-unit-effort basis using regression analysis with LT and HL as the dependent and independent variables, respectively. The average number of mosquitoes captured in 1 min by LT over a 24-h period was significantly related to the average number captured in 1 min by HL only for Cx. nigripalpus and Cx. quinquefasciatus. Patterns of diel activity indicated by a comparison of the mean response to LT and HL at eight different times in a 24-h period were not superposable for any species. The capture rate efficiency of LT when compared with HL was ≤15% for all mosquitoes except Cx. quinquefasciatus (43%). Statistical models of the relationship between mosquito responses to each collection method indicate that, except for Ae. albopictus, LT and HL capture rates are significantly related only during certain times of the diel period. Estimates of mosquito activity based on observations made between sunset and sunrise were most precise in this regard for An. quadrimaculatus and Cx. nigripalpus, as were those between sunrise and sunset for Cx. quinquefasciatus and Ae. triseriatus.
Diel mercury-concentration variations in streams affected by mining and geothermal discharge
Nimick, D.A.; McCleskey, R. Blaine; Gammons, C.H.; Cleasby, T.E.; Parker, S.R.
2007-01-01
Diel variations of concentrations of unfiltered and filtered total Hg and filtered methyl Hg were documented during 24-h sampling episodes in water from Silver Creek, which drains a historical gold-mining district near Helena, Montana, and the Madison River, which drains the geothermal system of Yellowstone National Park. The concentrations of filtered methyl Hg had relatively large diel variations (increases of 68 and 93% from morning minima) in both streams. Unfiltered and filtered (0.1-??m filtration) total Hg in Silver Creek had diel concentration increases of 24% and 7%, respectively. In the Madison River, concentrations of unfiltered and filtered total Hg did not change during the sampling period. The concentration variation of unfiltered total Hg in Silver Creek followed the diel variation in suspended-particle concentration. The concentration variation of filtered total and methyl Hg followed the solar photocycle, with highest concentrations during the early afternoon and evening and lowest concentrations during the morning. None of the diel Hg variations correlated with diel variation in streamflow or major ion concentrations. The diel variation in filtered total Hg could have been produced by adsorption-desorption of Hg2+ or by reduction of Hg(II) to Hg0 and subsequent evasion of Hg0. The diel variation in filtered methyl Hg could have been produced by sunlight- and temperature-dependent methylation. This study is the first to examine diel Hg cycling in streams, and its results reinforce previous conclusions that diel trace-element cycling in streams is widespread but often not recognized and that parts of the biogeochemical Hg cycle respond quickly to the daily photocycle. ?? 2006 Elsevier B.V. All rights reserved.
Summer microhabitat use of fluvial bull trout in Eastern Oregon streams
Al-Chokhachy, R.; Budy, P.
2007-01-01
The management and recovery of populations of bull trout Salvelinus confluentus requires a comprehensive understanding of habitat use across different systems, life stages, and life history forms. To address these needs, we collected microhabitat use and availability data in three fluvial populations of bull trout in eastern Oregon. We evaluated diel differences in microhabitat use, the consistency of microhabitat use across systems and size-classes based on preference, and our ability to predict bull trout microhabitat use. Diel comparisons suggested bull trout continue to use deeper microhabitats with cover but shift into significantly slower habitats during nighttime periods; however, we observed no discrete differences in substrate use patterns across diel periods. Across life stages, we found that both juvenile and adult bull trout used slow-velocity microhabitats with cover, but the use of specific types varied. Both logistic regression and habitat preference analyses suggested that adult bull trout used deeper habitats than juveniles. Habitat preference analyses suggested that bull trout habitat use was consistent across all three systems, as chi-square tests rejected the null hypotheses that microhabitats were used in proportion to those available (P < 0.0001). Validation analyses indicated that the logistic regression models (juvenile and adult) were effective at predicting bull trout absence across all tests (specificity values = 100%); however, our ability to accurately predict bull trout absence was limited (sensitivity values = 0% across all tests). Our results highlight the limitations of the models used to predict microhabitat use for fish species like bull trout, which occur at naturally low densities. However, our results also demonstrate that bull trout microhabitat use patterns are generally consistent across systems, a pattern that parallels observations at both similar and larger scales and across life history forms. Thus, our results, in combination with previous bull trout habitat studies, provide managers with benchmarks for restoration in highly degraded systems.
Kay, Robert T.; Groschen, George E.; Dupre, David H.; Drexler, Timothy D.; Thingvold, Karen L.; Rosenfeld, Heather J.
2009-01-01
Surface water can exhibit substantial diel variations in the concentration of a number of constituents. Sampling regimens that do not characterize diel variations in water quality can result in an inaccurate understanding of site conditions and of the threat posed by the site to human health and the environment. Surface- and groundwater affected by acid drainage were sampled every 60 to 90 minutes over a 48-hour period at a former zinc smelter known as the Hegeler Zinc Superfund Site, in Hegeler, Ill. Groundwater-quality data from a well at the site indicate stable, low pH, weakly oxidizing geochemical conditions in the aquifer. With the exceptions of temperature and pH, no constituents exhibited diel variations in groundwater. Variations in temperature and pH likely were not representative of conditions in the aquifer. Surface water was sampled at a site on Grape Creek. Diel variations were observed in temperature, dissolved oxygen, pH, and specific conductance, and in the concentrations of nitrite, barium, iron, lead, vanadium, and possibly uranium. Concentrations during the diel cycles varied by about an order of magnitude for nitrite and varied by about a factor of two for barium, iron, lead, vanadium, and uranium. Temperature, dissolved oxygen, specific conductance, nitrite, barium, lead, and uranium generally reached maximum values during the afternoon and minimum values during the night. Iron, vanadium, and pH generally reached minimum values during the afternoon and maximum values during the night. These variations would need to be accounted for during sampling of surface-water quality in similar hydrologic settings. The temperature variations in surface water were affected by variations in air temperature. Concentrations of dissolved oxygen were affected by variations in the intensity of photosynthetic activity and respiration. Nitrite likely was formed by the oxidation of ammonium by dissolved oxygen and degraded by its anaerobic oxidation by ammonium or as part of the decomposition of organic matter. Variations in pH were affected by the photoreduction of Fe3+ to Fe2+ and the precipitation of iron oxyhydroxides. Diel variations in concentrations of iron and vanadium were likely caused by variations in the dissolution and precipitation of iron oxyhydroxides, oxyhydroxysulfates, and hydrous sulfates, which may have been affected by in the intensity of insolation, iron photoreduction, and the concentration of dissolved oxygen. The concentrations of lead, uranium, and perhaps barium in Grape Creek may have been affected by competition for sorption sites on iron oxyhydroxides. Competition for sorption sites was likely affected by variations in pH and the concentration of Fe2+. Constituent concentrations likely also were affected by precipitation and dissolution of minerals that are sensitive to changes in pH, temperature, oxidation-reduction conditions, and biologic activity. The chemical and biologic processes that resulted in the diel variations observed in Grape Creek occurred within the surface-water column or in the underlying sediments.
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, and barium may have been affected by competition with Fe+2 for sorption sites on hydrous ferric oxide minerals. ?? 2010.
Iodine(III) Derivatives as Halogen Bonding Organocatalysts.
Heinen, Flemming; Engelage, Elric; Dreger, Alexander; Weiss, Robert; Huber, Stefan M
2018-03-26
Hypervalent iodine(III) derivatives are known as versatile reagents in organic synthesis, but there is only one previous report on their use as Lewis acidic organocatalysts. Herein, we present first strong indications for the crucial role of halogen bonding in this kind of catalyses. To this end, the solvolysis of benzhydryl chloride and the Diels-Alder reaction of cyclopentadiene with methyl vinyl ketone served as benchmark reactions for halide abstraction and the activation of neutral compounds. Iodolium compounds (cyclic diaryl iodonium species) were used as activators or catalysts, and we were able to markedly reduce or completely switch off their activity by sterically blocking one or two of their electrophilic axes. Compared with previously established bidentate cationic halogen bond donors, the monodentate organoiodine derivatives used herein are at least similarly active (in the Diels-Alder reaction) or even decidedly more active (in benzhydryl chloride solvolysis). © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Thermally cleavable surfactants
DOE Office of Scientific and Technical Information (OSTI.GOV)
McElhanon, James R; Simmons, Blake A; Zifer, Thomas
2009-11-24
Two new surfactant molecules are reported which contain thermally labile Diels-Alder adducts connecting the polar and non-polar sections of each molecule. The two surfactants possess identical non-polar dodecyl tail segments but exhibit different polar headgroups. The surfactants become soluble in water when anionic salts are formed through the deprotonation of the surfactant headgroups by the addition of potassium hydroxide. When either surfactant is exposed to temperature above about 60.degree. C., the retro Diels-Alder reaction occurs, yielding hydrophilic and hydrophobic fragments or the aqueous solutions of the surfactants subsequently exhibit loss of all surface-active behavior.
Thermally cleavable surfactants
DOE Office of Scientific and Technical Information (OSTI.GOV)
McElhanon, James R; Simmons, Blake A; Zifer, Thomas
2009-09-29
Two new surfactant molecules are reported which contain thermally labile Diels-Alder adducts connecting the polar and non-polar sections of each molecule. The two surfactants possess identical non-polar dodecyl tail segments but exhibit different polar headgroups. The surfactants become soluble in water when anionic salts are formed through the deprotonation of the surfactant headgroups by the addition of potassium hydroxide. When either surfactant is exposed to temperature above about 60.degree. C., the retro Diels-Alder reaction occurs, yielding hydrophilic and hydrophobic fragments or the aqueous solutions of the surfactants subsequently exhibit loss of all surface-active behavior.
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.
Thermally cleavable surfactants
McElhanon, James R [Manteca, CA; Simmons, Blake A [San Francisco, CA; Zifer, Thomas [Manteca, CA; Jamison, Gregory M [Albuquerque, NM; Loy, Douglas A [Albuquerque, NM; Rahimian, Kamyar [Albuquerque, NM; Long, Timothy M [Urbana, IL; Wheeler, David R [Albuquerque, NM; Staiger, Chad L [Albuquerque, NM
2006-04-04
Two new surfactant molecules are reported which contain thermally labile Diels-Alder adducts connecting the polar and non-polar sections of each molecule. The two surfactants possess identical non-polar dodecyl tail segments but exhibit different polar headgroups. The surfactants become soluble in water when anionic salts are formed through the deprotonation of the surfactant headgroups by the addition of potassium hydroxide. When either surfactant is exposed to temperature above about 60.degree. C., the retro Diels-Alder reaction occurs, yielding hydrophilic and hydrophobic fragments and the aqueous solutions of the surfactants subsequently exhibit loss of all surface-active behavior.
Francis, Malcolm P
2013-01-01
Juvenile rig (Mustelus lenticulatus) were internally tagged with acoustic transmitters and tracked with acoustic receivers deployed throughout two arms of Porirua Harbour, a small (7 km(2)) estuary in New Zealand. Ten rig were tracked for up to four months during summer-autumn to determine their spatial and temporal use of the habitat. The overall goal was to estimate the size of Marine Protected Areas required to protect rig nursery areas from direct human impacts. Rig showed clear site preferences, but those preferences varied among rig and over time. They spent most of their time in large basins and on shallow sand and mud flats around the margins, and avoided deep channels. Habitat range increased during autumn for many of the rig. Only one shark spent time in both harbour arms, indicating that there was little movement between the two. Rig home ranges were 2-7 km(2), suggesting that an effective MPA would need to cover the entire Porirua Harbour. They moved to outer harbour sites following some high river flow rates, and most left the harbour permanently during or soon after a river spike, suggesting that they were avoiding low salinity water. Rig showed strong diel movements during summer, although the diel pattern weakened in autumn. Persistent use of the same day and night sites indicates that diel movements are directed rather than random. Further research is required to determine the sizes of rig home ranges in larger harbours where nursery habitat is more extensive. Marine Protected Areas do not control land-based impacts such as accelerated sedimentation and heavy metal pollution, so integration of marine and terrestrial management tools across a range of government agencies is essential to fully protect nursery areas.
Zheng, Han; Wang, Qiufeng; Zhu, Xianjin; Li, Yingnian; Yu, Guirui
2014-01-01
Evapotranspiration (ET) is an important component of the water cycle in terrestrial ecosystems. Understanding the ways in which ET changes with meteorological factors is central to a better understanding of ecological and hydrological processes. In this study, we used eddy covariance measurements of ET from a typical alpine shrubland meadow ecosystem in China to investigate the hysteresis response of ET to environmental variables including air temperature (Ta), vapor pressure deficit (VPD) and net radiation (Rn) at a diel timescale. Meanwhile, the simulated ET by Priestly-Taylor equation was used to interpret the measured ET under well-watered conditions. Pronounced hysteresis was observed in both Ta and VPD response curves of ET. At a similar Ta and VPD, ET was always significantly depressed in the afternoon compared with the morning. But the hysteresis response of ET to Rn was not evident. Similar hysteresis patterns were also observed in the Ta/VPD response curves of simulated ET. The magnitudes of the measured and simulated hysteresis loops showed similar seasonal variation, with relatively smaller values occurring from May to September, which agreed well with the lifetime of plants and the period of rainy season at this site. About 62% and 23% of changes in the strength of measured ET-Ta and ET-VPD loops could be explained by the changes in the strength of simulated loops, respectively. Thus, the time lag between Rn and Ta/VPD is the most important factor generating and modulating the ET-Ta/VPD hysteresis, but plants and water status also contribute to the hysteresis response of ET. Our research confirmed the different hysteresis in the responses of ET to meteorological factors and proved the vital role of Rn in driving the diel course of ET.
Francis, Malcolm P.
2013-01-01
Juvenile rig (Mustelus lenticulatus) were internally tagged with acoustic transmitters and tracked with acoustic receivers deployed throughout two arms of Porirua Harbour, a small (7 km2) estuary in New Zealand. Ten rig were tracked for up to four months during summer–autumn to determine their spatial and temporal use of the habitat. The overall goal was to estimate the size of Marine Protected Areas required to protect rig nursery areas from direct human impacts. Rig showed clear site preferences, but those preferences varied among rig and over time. They spent most of their time in large basins and on shallow sand and mud flats around the margins, and avoided deep channels. Habitat range increased during autumn for many of the rig. Only one shark spent time in both harbour arms, indicating that there was little movement between the two. Rig home ranges were 2–7 km2, suggesting that an effective MPA would need to cover the entire Porirua Harbour. They moved to outer harbour sites following some high river flow rates, and most left the harbour permanently during or soon after a river spike, suggesting that they were avoiding low salinity water. Rig showed strong diel movements during summer, although the diel pattern weakened in autumn. Persistent use of the same day and night sites indicates that diel movements are directed rather than random. Further research is required to determine the sizes of rig home ranges in larger harbours where nursery habitat is more extensive. Marine Protected Areas do not control land-based impacts such as accelerated sedimentation and heavy metal pollution, so integration of marine and terrestrial management tools across a range of government agencies is essential to fully protect nursery areas. PMID:23437298
Parker, Stephen R.; Gammons, Christopher H.; Poulson, Simon R.; DeGrandpre, Michael D.
2007-01-01
Many rivers undergo diel (24-h) concentration fluctuations of pH, dissolved gases, trace metals, nutrients, and other chemical species. A study conducted in 1994 documented such behavior in the upper Clark Fork River, Montana, a stream whose headwaters have been severely impacted by historic metal mining, milling, and smelting. The purpose of the present investigation was to expand on these earlier findings by conducting simultaneous diel samplings at two sites on the upper Clark Fork River separated by 2.5 h of stream travel time. By monitoring two stations, it was possible to more closely examine the processes that control temporal and spatial gradients in stream chemistry. Another objective was to examine diel changes in the δ13C composition of dissolved inorganic C (DIC) and their relationship to biological activity in the stream. The most important findings of this study include: (1) concentrations of dissolved and particulate heavy metals increased during the night and decreased during the day, in agreement with previous work; (2) these changes were positively correlated to diel changes in pH, dissolved O2, and water temperature; (3) dissolved concentrations increased during the night at the lower site, but showed the opposite behavior at the upper site; and (4) diel changes in δ13C-DIC were noted at both sites, although the timing and magnitudes of the cycles differed. Hypotheses to explain the first two observations include: cyclic co-precipitation of divalent metals with carbonate minerals; pH- and temperature-dependent sorption of metal cations onto the streambed and suspended particles; or photosynthetically enhanced oxidation and removal of Fe and Mn oxides at biofilm surfaces during the daytime. The latter model explains the majority of the field observations, including night-time increases in particulate forms of Fe and other elements.
Gammons, C.H.; Nimick, D.A.; Parker, S.R.; Cleasby, T.E.; McCleskey, R. Blaine
2005-01-01
Three simultaneous 24-h samplings at three sites over a downstream pH gradient were conducted to examine diel fluctuations in heavy metal concentrations in Fisher Creek, a small mountain stream draining abandoned mine lands in Montana. Average pH values at the upstream (F1), middle (F2), and downstream (F3) monitoring stations were 3.31, 5.46, and 6.80, respectively. The downstream increase in pH resulted in precipitation of hydrous ferric oxide (HFO) and hydrous aluminum oxide (HAO) on the streambed. At F1 and F2, Fe showed strong diel cycles in dissolved concentration and Fe(II)/Fe(III) ratio; these cycles were attributed to daytime photoreduction of Fe(III) to Fe(II), reoxidation of Fe(II) to Fe(III), and temperature-dependent hydrolysis and precipitation of HFO. At the near-neutral downstream station, no evidence of Fe(III) photoreduction was observed, and suspended particles of HFO dominated the total Fe load. HFO precipitation rates between F2 and F3 were highest in the afternoon, due in part to reoxidation of a midday pulse of Fe2+ formed by photoreduction in the upper, acidic portions of the stream. Dissolved concentrations of Fe(II) and Cu decreased tenfold and 2.4-fold, respectively, during the day at F3. These changes were attributed to sorption onto fresh HFO surfaces. Results of surface complexation modeling showed good agreement between observed and predicted Cu concentrations at F3, but only when adsorption enthalpies were added to the thermodynamic database to take into account diel temperature variations. The field and modeling results illustrate that the degree to which trace metals adsorb onto actively forming HFO is strongly temperature dependent. This study is an example of how diel Fe cycles caused by redox and hydrolysis reactions can induce a diel cycle in a trace metal of toxicological importance in downstream waters. Copyright ?? 2005 Elsevier Ltd.
Diel cycling of trace elements in streams draining mineralized areas: a review
Gammons, Christopher H.; Nimick, David A.; Parker, Stephen R.
2015-01-01
Many trace elements exhibit persistent diel, or 24-h, concentration cycles in streams draining mineralized areas. These cycles can be caused by various physical and biogeochemical mechanisms including streamflow variation, photosynthesis and respiration, as well as reactions involving photochemistry, adsorption and desorption, mineral precipitation and dissolution, and plant assimilation. Iron is the primary trace element that exhibits diel cycling in acidic streams. In contrast, many cationic and anionic trace elements exhibit diel cycling in near-neutral and alkaline streams. Maximum reported changes in concentration for these diel cycles have been as much as a factor of 10 (988% change in Zn concentration over a 24-h period). Thus, monitoring and scientific studies must account for diel trace-element cycling to ensure that water-quality data collected in streams appropriately represent the conditions intended to be studied.
Flexible foraging movements of leatherback turtles across the North Atlantic Ocean.
Hays, Graeme C; Hobson, Victoria J; Metcalfe, Julian D; Righton, David; Sims, David W
2006-10-01
Some marine species have been shown to target foraging at particular hotspots of high prey abundance. However, we show here that in the year after a nesting season, female leatherback turtles (Dermochelys coriacea) in the Atlantic generally spend relatively little time in fixed hotspots, especially those with a surface signature revealed in satellite imagery, but rather tend to have a pattern of near continuous traveling. Associated with this traveling, distinct changes in dive behavior indicate that turtles constantly fine tune their foraging behavior and diel activity patterns in association with local conditions. Switches between nocturnal vs. diurnal activity are rare in the animal kingdom but may be essential for survival on a diet of gelatinous zooplankton where patches of high prey availability are rare. These results indicate that in their first year after nesting, leatherback turtles do not fit the general model of migration where responses to resources are suppressed during transit. However, their behavior may be different in their sabbatical years away from nesting beaches. Our results highlight the importance of whole-ocean fishing gear regulations to minimize turtle bycatch.
NASA Astrophysics Data System (ADS)
Song, W.; Staudt, M.; Bourgeois, I.; Williams, J.
2014-03-01
Plants emit significant amounts of monoterpenes into the earth's atmosphere, where they react rapidly to form a multitude of gas phase species and particles. Many monoterpenes exist in mirror-image forms or enantiomers. In this study the enantiomeric monoterpene profile for several representative plants (Quercus ilex L., Rosmarinus officinalis L., and Pinus halepensis Mill.) was investigated as a function of chemotype, light and temperature both in the laboratory and in the field. Analysis of enantiomeric monoterpenes from 19 Quercus ilex individuals from Southern France and Spain revealed four regiospecific chemotypes (genetically fixed emission patterns). In agreement with previous work, only Quercus ilex emissions increased strongly with light. However, for all three plant species no consistent enantiomeric variation was observed as a function of light, and the enantiomeric ratio of α-pinene was found to vary by less than 20% from 100 and 1000 μmol m-2 s-1 PAR (photosynthetically active radiation). The rate of monoterpene emission increased with temperature from all three plant species, but little variation in the enantiomeric distribution of α-pinene was observed with temperature. There was more enantiomeric variability between individuals of the same species than could be induced by either light or temperature. Field measurements of α-pinene enantiomer mixing ratios in the air, taken at a Quercus ilex forest in Southern France, and several other previously reported field enantiomeric ratio diel cycle profiles are compared. All show smoothly varying diel cycles (some positive and some negative) even over changing wind directions. This is surprising in comparison with variations of enantiomeric emission patterns shown by individuals of the same species.
Habibi, Ghader; Ajory, Neda
2015-11-01
Photosynthesis is a biological process most affected by water deficit. Plants have various photosynthetic mechanisms that are matched to specific climatic zones. We studied the photosynthetic plasticity of C3 plants at water deficit using ecotypes of Marrubium vulgare L. from high (2,200 m) and low (1,100 m) elevation sites in the Mishou-Dagh Mountains of Iran. Under experimental drought, high-altitude plants showed more tolerance to water stress based on most of the parameters studied as compared to the low-altitude plants. Increased tolerance in high-altitude plants was achieved by lower levels of daytime stomatal conductance (g s) and reduced damaging effect on maximal quantum yield of photosystem II (PSII) (F v /F m ) coupled with higher levels of carotenoids and non-photochemical quenching (NPQ). High-altitude plants exhibited higher water use efficiency (WUE) than that in low-altitude plants depending on the presence of thick leaves and the reduced daytime stomatal conductance. Additionally, we have studied the oscillation in H(+) content and diel gas exchange patterns to determine the occurrence of C3 or weak CAM (Crassulacean acid metabolism) in M. vulgare through 15 days drought stress. Under water-stressed conditions, low-altitude plants exhibited stomatal conductance and acid fluctuations characteristic of C3 photosynthesis, though high-altitude plants exhibited more pronounced increases in nocturnal acidity and phosphoenolpyruvate carboxylase (PEPC) activity, suggesting photosynthetic flexibility. These results indicated that the regulation of carotenoids, NPQ, stomatal conductance and diel patterns of CO2 exchange presented the larger differences among studied plants at different altitudes and seem to be the protecting mechanisms controlling the photosynthetic performance of M. vulgare plants under drought conditions.
Cheung, C Y Maurice; Poolman, Mark G; Fell, David A; Ratcliffe, R George; Sweetlove, Lee J
2014-06-01
Although leaves have to accommodate markedly different metabolic flux patterns in the light and the dark, models of leaf metabolism based on flux-balance analysis (FBA) have so far been confined to consideration of the network under continuous light. An FBA framework is presented that solves the two phases of the diel cycle as a single optimization problem and, thus, provides a more representative model of leaf metabolism. The requirement to support continued export of sugar and amino acids from the leaf during the night and to meet overnight cellular maintenance costs forces the model to set aside stores of both carbon and nitrogen during the day. With only minimal constraints, the model successfully captures many of the known features of C 3 leaf metabolism, including the recently discovered role of citrate synthesis and accumulation in the night as a precursor for the provision of carbon skeletons for amino acid synthesis during the day. The diel FBA model can be applied to other temporal separations, such as that which occurs in Crassulacean acid metabolism (CAM) photosynthesis, allowing a system-level analysis of the energetics of CAM. The diel model predicts that there is no overall energetic advantage to CAM, despite the potential for suppression of photorespiration through CO 2 concentration. Moreover, any savings in enzyme machinery costs through suppression of photorespiration are likely to be offset by the higher flux demand of the CAM cycle. It is concluded that energetic or nitrogen use considerations are unlikely to be evolutionary drivers for CAM photosynthesis. © 2014 American Society of Plant Biologists. All Rights Reserved.
Cheung, C.Y. Maurice; Poolman, Mark G.; Fell, David. A.; Ratcliffe, R. George; Sweetlove, Lee J.
2014-01-01
Although leaves have to accommodate markedly different metabolic flux patterns in the light and the dark, models of leaf metabolism based on flux-balance analysis (FBA) have so far been confined to consideration of the network under continuous light. An FBA framework is presented that solves the two phases of the diel cycle as a single optimization problem and, thus, provides a more representative model of leaf metabolism. The requirement to support continued export of sugar and amino acids from the leaf during the night and to meet overnight cellular maintenance costs forces the model to set aside stores of both carbon and nitrogen during the day. With only minimal constraints, the model successfully captures many of the known features of C3 leaf metabolism, including the recently discovered role of citrate synthesis and accumulation in the night as a precursor for the provision of carbon skeletons for amino acid synthesis during the day. The diel FBA model can be applied to other temporal separations, such as that which occurs in Crassulacean acid metabolism (CAM) photosynthesis, allowing a system-level analysis of the energetics of CAM. The diel model predicts that there is no overall energetic advantage to CAM, despite the potential for suppression of photorespiration through CO2 concentration. Moreover, any savings in enzyme machinery costs through suppression of photorespiration are likely to be offset by the higher flux demand of the CAM cycle. It is concluded that energetic or nitrogen use considerations are unlikely to be evolutionary drivers for CAM photosynthesis. PMID:24596328
Effects of subsampling of passive acoustic recordings on acoustic metrics.
Thomisch, Karolin; Boebel, Olaf; Zitterbart, Daniel P; Samaran, Flore; Van Parijs, Sofie; Van Opzeeland, Ilse
2015-07-01
Passive acoustic monitoring is an important tool in marine mammal studies. However, logistics and finances frequently constrain the number and servicing schedules of acoustic recorders, requiring a trade-off between deployment periods and sampling continuity, i.e., the implementation of a subsampling scheme. Optimizing such schemes to each project's specific research questions is desirable. This study investigates the impact of subsampling on the accuracy of two common metrics, acoustic presence and call rate, for different vocalization patterns (regimes) of baleen whales: (1) variable vocal activity, (2) vocalizations organized in song bouts, and (3) vocal activity with diel patterns. To this end, above metrics are compared for continuous and subsampled data subject to different sampling strategies, covering duty cycles between 50% and 2%. The results show that a reduction of the duty cycle impacts negatively on the accuracy of both acoustic presence and call rate estimates. For a given duty cycle, frequent short listening periods improve accuracy of daily acoustic presence estimates over few long listening periods. Overall, subsampling effects are most pronounced for low and/or temporally clustered vocal activity. These findings illustrate the importance of informed decisions when applying subsampling strategies to passive acoustic recordings or analyses for a given target species.
NASA Astrophysics Data System (ADS)
Blumenthal, J. M.; Austin, T. J.; Bothwell, J. B.; Broderick, A. C.; Ebanks-Petrie, G.; Olynik, J. R.; Orr, M. F.; Solomon, J. L.; Witt, M. J.; Godley, B. J.
2009-03-01
As historically abundant spongivores, hawksbill turtles Eretmochelys imbricata likely played a key ecological role on coral reefs. However, coral reefs are now experiencing global declines and many hawksbill populations are critically reduced. For endangered species, tracking movement has been recognized as fundamental to management. Since movements in marine vertebrates encompass three dimensions, evaluation of diving behavior and range is required to characterize marine turtle habitat. In this study, habitat use of hawksbill turtles on a Caribbean coral reef was elucidated by quantifying diel depth utilization and movements in relation to the boundaries of marine protected areas. Time depth recorders (TDRs) and ultrasonic tags were deployed on 21 Cayman Islands hawksbills, ranging in size from 26.4 to 58.4 cm straight carapace length. Study animals displayed pronounced diel patterns of diurnal activity and nocturnal resting, where diurnal dives were significantly shorter, deeper, and more active. Mean diurnal dive depth (±SD) was 8 ± 5 m, range 2-20 m, mean nocturnal dive depth was 5 ± 5 m, range 1-14 m, and maximum diurnal dive depth was 43 ± 27 m, range 7-91 m. Larger individuals performed significantly longer dives. Body mass was significantly correlated with mean dive depth for nocturnal but not diurnal dives. However, maximum diurnal dive depth was significantly correlated with body mass, suggesting partitioning of vertical habitat by size. Thus, variable dive capacity may reduce intraspecific competition and provide resistance to degradation in shallow habitats. Larger hawksbills may also represent important predators on deep reefs, creating a broad ecological footprint over a range of depths.
The influence of sea ice, wind speed and marine mammals on Southern Ocean ambient sound.
Menze, Sebastian; Zitterbart, Daniel P; van Opzeeland, Ilse; Boebel, Olaf
2017-01-01
This paper describes the natural variability of ambient sound in the Southern Ocean, an acoustically pristine marine mammal habitat. Over a 3-year period, two autonomous recorders were moored along the Greenwich meridian to collect underwater passive acoustic data. Ambient sound levels were strongly affected by the annual variation of the sea-ice cover, which decouples local wind speed and sound levels during austral winter. With increasing sea-ice concentration, area and thickness, sound levels decreased while the contribution of distant sources increased. Marine mammal sounds formed a substantial part of the overall acoustic environment, comprising calls produced by Antarctic blue whales ( Balaenoptera musculus intermedia ), fin whales ( Balaenoptera physalus ), Antarctic minke whales ( Balaenoptera bonaerensis ) and leopard seals ( Hydrurga leptonyx ). The combined sound energy of a group or population vocalizing during extended periods contributed species-specific peaks to the ambient sound spectra. The temporal and spatial variation in the contribution of marine mammals to ambient sound suggests annual patterns in migration and behaviour. The Antarctic blue and fin whale contributions were loudest in austral autumn, whereas the Antarctic minke whale contribution was loudest during austral winter and repeatedly showed a diel pattern that coincided with the diel vertical migration of zooplankton.
Diel and spatial patterns in the singing behavior of humpback whales off Oahu, Hawaii
NASA Astrophysics Data System (ADS)
Lammers, Marc O.; Stimpert, Alison K.; Au, Whitlow W. L.; Mooney, T. Aran
2005-09-01
The singing behavior of male humpback whales on the winter breeding grounds is still a poorly understood phenomenon. Previous work indicates that the chorusing levels of singing whales off west Maui are higher at night than during the day. However, the cause of this variation is not known. To investigate whether more whales sing at night or whether the same number simply move closer to near-shore recorders following sunset, the abundance and location of singing whales off Kaena Point, Oahu was examined. A bottom-moored recording system was used to establish that the same diel pattern observed off Maui also occurs off Oahu. The location of singing whales was determined by localizing singers along a preset transect track using a towed hydrophone array. More whales were found singing along the coastline examined at night than during the day. There was no indication of a shoreward migration. These results suggest that, at night, singing displays may be a more effective behavioral tactic than direct competition in a pod. Also, more singers were found along the northern part of the coastline, which is dominated by a shallow bank, indicating that singers were selective with respect to where they chose to sing.
Warren, M A; Morbey, Y E
2012-09-01
Diel patterns of migration and migration speed were compared between reproductive timing phenotypes in female kokanee salmon Oncorhynchus nerka. Females of varying degrees of reproductive maturation were captured on their migration route to the Meadow Creek Spawning Channel (British Columbia, Canada), were tagged with passive-integrated transponders (PIT tags) and were subsequently monitored with stationary receivers. Females showed crepuscular migration timing, with approximately equal detections at dawn and dusk. In particular, peaks of movement were associated with the appearance of the sun over the mountains in the east and the disappearance of the sun over the mountains in the west. Over 25 m, migration speed was 1·0 body lengths (measured as fork length; L(F)) s(-1) and did not depend on maturation state. Over 3 km, migration speed was much slower (0·2-0·3 L(F) s(-1)) than over the short distance, with less mature females migrating more slowly than more mature females. Less mature females appeared to be in less of a hurry to reach breeding areas compared with more mature females. © 2012 The Authors. Journal of Fish Biology © 2012 The Fisheries Society of the British Isles.
The influence of sea ice, wind speed and marine mammals on Southern Ocean ambient sound
NASA Astrophysics Data System (ADS)
Menze, Sebastian; Zitterbart, Daniel P.; van Opzeeland, Ilse; Boebel, Olaf
2017-01-01
This paper describes the natural variability of ambient sound in the Southern Ocean, an acoustically pristine marine mammal habitat. Over a 3-year period, two autonomous recorders were moored along the Greenwich meridian to collect underwater passive acoustic data. Ambient sound levels were strongly affected by the annual variation of the sea-ice cover, which decouples local wind speed and sound levels during austral winter. With increasing sea-ice concentration, area and thickness, sound levels decreased while the contribution of distant sources increased. Marine mammal sounds formed a substantial part of the overall acoustic environment, comprising calls produced by Antarctic blue whales (Balaenoptera musculus intermedia), fin whales (Balaenoptera physalus), Antarctic minke whales (Balaenoptera bonaerensis) and leopard seals (Hydrurga leptonyx). The combined sound energy of a group or population vocalizing during extended periods contributed species-specific peaks to the ambient sound spectra. The temporal and spatial variation in the contribution of marine mammals to ambient sound suggests annual patterns in migration and behaviour. The Antarctic blue and fin whale contributions were loudest in austral autumn, whereas the Antarctic minke whale contribution was loudest during austral winter and repeatedly showed a diel pattern that coincided with the diel vertical migration of zooplankton.
Phytochemical, cytotoxic and chemotaxonomic study on Ajuga forrestii Diels (Labiatae).
Chen, Tong; Diao, Qing-Yan; Yu, Hai-Zhou; Jiao, Chun-Li; Ruan, Jian
2018-04-01
A phytochemical investigation of Ajuga forrestii Diels led to the isolation of 14 compounds, including eight neo-clerodane diterpenes (1-8), two phytoecdysteroids (9, 11), one stigmastane sterol (10) and three iridoid glycosides (12-14). The structures of these compounds were identified by spectroscopic methods and a comparison of their data with those reported in the literature. This is the first report of compounds 1-14 from A. forrestii. The cytotoxic activities of the aqueous extract of A. forrestii and several compounds have been studied and the chemotaxonomic significance of isolated compounds has also been summarised.
Salgueiro, Daniela A L; Sousa, Cristina E A; Fortes, A Gil; Alves, M José
2012-12-01
This comprehensive review deals with the synthesis of 1-azafagomine, analogs, and derivatives having the Diels-Alder cycloaddition as the key step. Most of the compounds referred are racemic or have been resolved by lipase transesterification. There are two asymmetric cycloadditions leading to 1-azafagomine or to an analog. In one case both enantiomers of 1-azafagomine were prepared together with a pair of derivatives. The study comprises glycosidase inhibition studies of the target compounds to a set of glycosidic enzymes, and evidenced molecular features that enhance or diminish their activity as glycosidase inhibitors.
Rain reverses diel activity rhythms in an estuarine teleost
Payne, Nicholas L.; van der Meulen, Dylan E.; Gannon, Ruan; Semmens, Jayson M.; Suthers, Iain M.; Gray, Charles A.; Taylor, Matthew D.
2013-01-01
Activity rhythms are ubiquitous in nature, and generally synchronized with the day–night cycle. Several taxa have been shown to switch between nocturnal and diurnal activity in response to environmental variability, and these relatively uncommon switches provide a basis for greater understanding of the mechanisms and adaptive significance of circadian (approx. 24 h) rhythms. Plasticity of activity rhythms has been identified in association with a variety of factors, from changes in predation pressure to an altered nutritional or social status. Here, we report a switch in activity rhythm that is associated with rainfall. Outside periods of rain, the estuarine-associated teleost Acanthopagrus australis was most active and in shallower depths during the day, but this activity and depth pattern was reversed in the days following rain, with diurnality restored as estuarine conductivity and turbidity levels returned to pre-rain levels. Although representing the first example of a rain-induced reversal of activity rhythm in an aquatic animal of which we are aware, our results are consistent with established models on the trade-offs between predation risk and foraging efficiency. PMID:23173211
A facile microwave-assisted Diels-Alder reaction of vinylboronates.
Sarotti, Ariel M; Pisano, Pablo L; Pellegrinet, Silvina C
2010-11-21
The Diels-Alder reaction of vinylboronates can be easily performed using microwave irradiation giving excellent yields of the cycloadducts. Pinacol vinylboronate was the reagent of choice due to its stability towards hydrolysis, operational simplicity and yields of Diels-Alder products. To the best of our knowledge, this is the first example of microwave-assisted Diels-Alder reaction of boron-substituted dienophiles. Subsequent in situ oxidation of the cycloadducts with alkaline hydrogen peroxide afforded the alcohols efficiently.
Poulson, S.R.; Sullivan, A.B.
2009-01-01
The upper Klamath River experiences a cyanobacterial algal bloom and poor water quality during the summer. Diel chemical and isotopic techniques have been employed in order to investigate the rates of biogeochemical processes. Four diel measurements of field parameters (temperature, pH, dissolved oxygen concentrations, and alkalinity) and stable isotope compositions (dissolved oxygen-??18O and dissolved inorganic carbon-??13C) have been performed between June 2007 and August 2008. Significant diel variations of pH, dissolved oxygen (DO) concentration, and DO-??18O were observed, due to varying rates of primary productivity vs. respiration vs. gas exchange with air. Diel cycles are generally similar to those previously observed in river systems, although there are also differences compared to previous studies. In large part, these different diel signatures are the result of the low turbulence of the upper Klamath River. Observed changes in the diel signatures vs. sampling date reflect the evolution of the status of the algal bloom over the course of the summer. Results indicate the potential utility of applying diel chemical and stable isotope techniques to investigate the rates of biogeochemical cycles in slow-moving rivers, lakes, and reservoirs, but also illustrate the increased complexity of stable isotope dynamics in these low-turbulence systems compared to well-mixed aquatic systems. ?? 2009 Elsevier B.V.
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.
Diels-Alderase-free, bis-pericyclic, [4+2] dimerization in the biosynthesis of (±)-paracaseolide A
NASA Astrophysics Data System (ADS)
Wang, Tao; Hoye, Thomas R.
2015-08-01
The natural product paracaseolide A is a tetracyclic dilactone containing six adjacent stereocentres. Its skeleton occupies a unique structural space among the >200,000 characterized secondary metabolites. Six different research groups have reported a chemical synthesis of this compound, five of which used a thermal, net Diels-Alder [4+2] cycloaddition and dehydration at 110 °C to access the target by dimerization of a simple butenolide precursor. Here, we report that this dimerization proceeds under much milder conditions and with a different stereochemical outcome than previously recognized. This can be rationalized by invoking a bis-pericyclic transition state. Furthermore, we find that spontaneous epimerization, necessary to correct the configuration at one key stereocentre, is viable and that natural paracaseolide A is racemic. Together, these facts point to the absence of enzymatic catalysis (that is, Diels-Alderase activity) in the cycloaddition and strongly suggest that a non-enzyme-mediated dimerization is the actual event by which paracaseolide A is produced in nature.
Bai, Jing; Shi, Zixing
2017-08-16
Pristine carbon nanotubes (CNTs) were activated to exhibit Diels-Alder (DA) reactivity in a polymer matrix, which was modified with monomers containing furan groups. The DA-active polymer matrix was transferred into a dynamic reversible cross-linked inorganic-organic network via a Diels-Alder reaction with CNTs, where pristine CNTs were used as dienophile chemicals and furan-modified SBS acted as the macromolecular diene. In this system, the mechanical properties as well as resilience and solvent resistance were greatly improved even with the presence of only 1 wt % CNTs. Meanwhile, the hybrids retained recyclability and exhibited some smart behaviors, including self-healing and reprogrammable shape memory properties. Furthermore, due to the photothermal effect of CNTs, a retro-Diels-Alder (rDA) reaction was activated under laser irradiation, and healing of a crack on the hybrid surface was demonstrated in approximately 10 s with almost complete recovery of the mechanical properties. Such fast and efficient self-healing performance provides a new concept in designing self-healing nanocomposites with tunable structures and mechanical properties. Furthermore, the DA and rDA reactions could be combined to reprogram the shape memory behavior under laser irradiation or thermal treatment, wherein the temporary shape of the sample could be transferred to a permanent shape via the rDA reaction at high temperature.
Behavioral responses of Atlantic cod to sea temperature changes.
Freitas, Carla; Olsen, Esben Moland; Moland, Even; Ciannelli, Lorenzo; Knutsen, Halvor
2015-05-01
Understanding responses of marine species to temperature variability is essential to predict impacts of future climate change in the oceans. Most ectotherms are expected to adjust their behavior to avoid extreme temperatures and minimize acute changes in body temperature. However, measuring such behavioral plasticity in the wild is challenging. Combining 4 years of telemetry-derived behavioral data on juvenile and adult (30-80 cm) Atlantic cod (Gadus morhua), and in situ ocean temperature measurements, we found a significant effect of sea temperature on cod depth use and activity level in coastal Skagerrak. During summer, cod were found in deeper waters when sea surface temperature increased. Further, this effect of temperature was stronger on larger cod. Diel vertical migration, which consists in a nighttime rise to shallow feeding habitats, was stronger among smaller cod. As surface temperature increased beyond ∼15°C, their vertical migration was limited to deeper waters. In addition to larger diel vertical migrations, smaller cod were more active and travelled larger distances compared to larger specimens. Cold temperatures during winter tended, however, to reduce the magnitude of diel vertical migrations, as well as the activity level and distance moved by those smaller individuals. Our findings suggest that future and ongoing rises in sea surface temperature may increasingly deprive cod in this region from shallow feeding areas during summer, which may be detrimental for local populations of the species.
Behavioral responses of Atlantic cod to sea temperature changes
Freitas, Carla; Olsen, Esben Moland; Moland, Even; Ciannelli, Lorenzo; Knutsen, Halvor
2015-01-01
Understanding responses of marine species to temperature variability is essential to predict impacts of future climate change in the oceans. Most ectotherms are expected to adjust their behavior to avoid extreme temperatures and minimize acute changes in body temperature. However, measuring such behavioral plasticity in the wild is challenging. Combining 4 years of telemetry-derived behavioral data on juvenile and adult (30–80 cm) Atlantic cod (Gadus morhua), and in situ ocean temperature measurements, we found a significant effect of sea temperature on cod depth use and activity level in coastal Skagerrak. During summer, cod were found in deeper waters when sea surface temperature increased. Further, this effect of temperature was stronger on larger cod. Diel vertical migration, which consists in a nighttime rise to shallow feeding habitats, was stronger among smaller cod. As surface temperature increased beyond ∼15°C, their vertical migration was limited to deeper waters. In addition to larger diel vertical migrations, smaller cod were more active and travelled larger distances compared to larger specimens. Cold temperatures during winter tended, however, to reduce the magnitude of diel vertical migrations, as well as the activity level and distance moved by those smaller individuals. Our findings suggest that future and ongoing rises in sea surface temperature may increasingly deprive cod in this region from shallow feeding areas during summer, which may be detrimental for local populations of the species. PMID:26045957
Widespread iron limitation of phytoplankton in the south pacific ocean
Behrenfeld; Kolber
1999-02-05
Diel fluorescence patterns were discovered in phytoplankton sampled over 7000 kilometers of the South Pacific Ocean that appear indicative of iron-limiting growth conditions. These patterns were rapidly lost after in situ iron enrichment and were not observed during a 15,000-kilometer transect in the Atlantic Ocean where iron concentrations are relatively high. Laboratory studies of marine Synechococcus sp. indicated that the patterns in the South Pacific are a unique manifestation of iron limitation on the fluorescence signature of state transitions. Results suggest that primary productivity is iron limited not only throughout the equatorial Pacific but also over much of the vast South Pacific gyre.
Black-footed ferrets and Siberian polecats as ecological surrogates and ecological equivalents
Biggins, D.E.; Hanebury, L.R.; Miller, B.J.; Powell, R.A.
2011-01-01
Ecologically equivalent species serve similar functions in different communities, and an ecological surrogate species can be used as a substitute for an equivalent species in a community. Siberian polecats (Mustela eversmanii) and black-footed ferrets (M. nigripes) have long been considered ecological equivalents. Polecats also have been used as investigational surrogates for black-footed ferrets, yet the similarities and differences between the 2 species are poorly understood. We contrasted activity patterns of radiotagged polecats and ferrets released onto ferret habitat. Ferrets tended to be nocturnal and most active after midnight. Polecats were not highly selective for any period of the day or night. Ferrets and polecats moved most during brightly moonlit nights. The diel activity pattern of ferrets was consistent with avoidance of coyotes (Canis latrans) and diurnal birds of prey. Similarly, polecat activity was consistent with avoidance of red foxes (Vulpes vulpes) in their natural range. Intraguild predation (including interference competition) is inferred as a selective force influencing behaviors of these mustelines. Examination of our data suggests that black-footed ferrets and Siberian polecats might be ecological equivalents but are not perfect surrogates. Nonetheless, polecats as surrogates for black-footed ferrets have provided critical insight needed, especially related to predation, to improve the success of ferret reintroductions. ?? 2011 American Society of Mammalogists.
Peeters, Frank; Atamanchuk, Dariia; Tengberg, Anders; Encinas-Fernández, Jorge; Hofmann, Hilmar
2016-01-01
Lake metabolism is a key factor for the understanding of turnover of energy and of organic and inorganic matter in lake ecosystems. Long-term time series on metabolic rates are commonly estimated from diel changes in dissolved oxygen. Here we present long-term data on metabolic rates based on diel changes in total dissolved inorganic carbon (DIC) utilizing an open-water diel CO2-technique. Metabolic rates estimated with this technique and the traditional diel O2-technique agree well in alkaline Lake Illmensee (pH of ~8.5), although the diel changes in molar CO2 concentrations are much smaller than those of the molar O2 concentrations. The open-water diel CO2- and diel O2-techniques provide independent measures of lake metabolic rates that differ in their sensitivity to transport processes. Hence, the combination of both techniques can help to constrain uncertainties arising from assumptions on vertical fluxes due to gas exchange and turbulent diffusion. This is particularly important for estimates of lake respiration rates because these are much more sensitive to assumptions on gradients in vertical fluxes of O2 or DIC than estimates of lake gross primary production. Our data suggest that it can be advantageous to estimate respiration rates assuming negligible gradients in vertical fluxes rather than including gas exchange with the atmosphere but neglecting vertical mixing in the water column. During two months in summer the average lake net production was close to zero suggesting at most slightly autotrophic conditions. However, the lake emitted O2 and CO2 during the entire time period suggesting that O2 and CO2 emissions from lakes can be decoupled from the metabolism in the near surface layer.
Partial diel migration: A facultative migration underpinned by long-term inter-individual variation.
Harrison, Philip M; Gutowsky, Lee F G; Martins, Eduardo G; Patterson, David A; Cooke, Steven J; Power, Michael
2017-09-01
The variations in migration that comprise partial diel migrations, putatively occur entirely as a consequence of behavioural flexibility. However, seasonal partial migrations are increasingly recognised to be mediated by a combination of reversible plasticity in response to environmental variation and individual variation due to genetic and environmental effects. Here, we test the hypothesis that while partial diel migration heterogeneity occurs primarily due to short-term within-individual flexibility in behaviour, long-term individual differences in migratory behaviour also underpin this migration variation. Specifically, we use a hierarchical behavioural reaction norm approach to partition within- and among-individual variation in depth use and diel plasticity in depth use, across short- and long-term time-scales, in a group of 47 burbot (Lota lota) tagged with depth-sensing acoustic telemetry transmitters. We found that within-individual variation at the among-dates-within-seasons and among-seasons scale, explained the dominant proportion of phenotypic variation. However, individuals also repeatedly differed in their expression of migration behaviour over the 2 year study duration. These results reveal that diel migration variation occurs primarily due to short-term within-individual flexibility in depth use and diel migration behaviour. However, repeatable individual differences also played a key role in mediating partial diel migration. These findings represent a significant advancement of our understanding of the mechanisms generating the important, yet poorly understood phenomena of partial diel migration. Moreover, given the pervasive occurrence of diel migrations across aquatic taxa, these findings indicate that individual differences have an important, yet previously unacknowledged role in structuring the temporal and vertical dynamics of aquatic ecosystems. © 2017 The Authors. Journal of Animal Ecology © 2017 British Ecological Society.
Peeters, Frank; Atamanchuk, Dariia; Tengberg, Anders; Encinas-Fernández, Jorge; Hofmann, Hilmar
2016-01-01
Lake metabolism is a key factor for the understanding of turnover of energy and of organic and inorganic matter in lake ecosystems. Long-term time series on metabolic rates are commonly estimated from diel changes in dissolved oxygen. Here we present long-term data on metabolic rates based on diel changes in total dissolved inorganic carbon (DIC) utilizing an open-water diel CO2-technique. Metabolic rates estimated with this technique and the traditional diel O2-technique agree well in alkaline Lake Illmensee (pH of ~8.5), although the diel changes in molar CO2 concentrations are much smaller than those of the molar O2 concentrations. The open-water diel CO2- and diel O2-techniques provide independent measures of lake metabolic rates that differ in their sensitivity to transport processes. Hence, the combination of both techniques can help to constrain uncertainties arising from assumptions on vertical fluxes due to gas exchange and turbulent diffusion. This is particularly important for estimates of lake respiration rates because these are much more sensitive to assumptions on gradients in vertical fluxes of O2 or DIC than estimates of lake gross primary production. Our data suggest that it can be advantageous to estimate respiration rates assuming negligible gradients in vertical fluxes rather than including gas exchange with the atmosphere but neglecting vertical mixing in the water column. During two months in summer the average lake net production was close to zero suggesting at most slightly autotrophic conditions. However, the lake emitted O2 and CO2 during the entire time period suggesting that O2 and CO2 emissions from lakes can be decoupled from the metabolism in the near surface layer. PMID:28002477
NASA Astrophysics Data System (ADS)
Liu, Lian; Yang, Pengfei; Li, Junying; Zhang, Zhiliang; Yu, Xi; Lu, Ling
2017-05-01
Sliver nanoparticles (AgNPs) were synthesized and functionalized with furan group on their surface, followed by the reverse Diels-Alder (DA) reaction with bismaleimide to vary the particle size, so as to give different antibacterial activities. These nanoparticles were characterized using Scanning Electron Microscope (SEM), X-Ray Diffraction (XRD), Ultraviolet-Visible (UV-vis), Nanoparticle Size Analyzer and X-Ray Photoelectron Spectroscopy (XPS). It was found that the cross-linking reaction with bismaleimide had a great effect on the size of AgNPs. The size of the AgNPs could be controlled by the temperature of DA/r-DA equilibrium. The antibacterial activity was assessed using the inhibition zone diameter by introducing the particles into a media containing Escherichia coli, Listeria monocytogenes, and Staphylococcus aureus, respectively. It was found that these particles were effective bactericides. Furthermore, the antibacterial activity of the nanoparticles decreased orderly as the particle size enlarged.
Diels-Alder active-template synthesis of rotaxanes and metal-ion-switchable molecular shuttles.
Crowley, James D; Hänni, Kevin D; Leigh, David A; Slawin, Alexandra M Z
2010-04-14
A synthesis of [2]rotaxanes in which Zn(II) or Cu(II) Lewis acids catalyze a Diels-Alder cycloaddition to form the axle while simultaneously acting as the template for the assembly of the interlocked molecules is described. Coordination of the Lewis acid to a multidentate endotopic 2,6-di(methyleneoxymethyl)pyridyl- or bipyridine-containing macrocycle orients a chelated dienophile through the macrocycle cavity. Lewis acid activation of the double bond causes it to react with an incoming "stoppered" diene, affording the [2]rotaxane in up to 91% yield. Unusually for an active-template synthesis, the metal binding site "lives on" in these rotaxanes. This was exploited in the synthesis of a molecular shuttle containing two different ligating sites in which the position of the macrocycle could be switched by complexation with metal ions [Zn(II) and Pd(II)] with different preferred coordination geometries.
Increased Diels-Alderase activity through backbone remodeling guided by Foldit players.
Eiben, Christopher B; Siegel, Justin B; Bale, Jacob B; Cooper, Seth; Khatib, Firas; Shen, Betty W; Players, Foldit; Stoddard, Barry L; Popovic, Zoran; Baker, David
2012-01-22
Computational enzyme design holds promise for the production of renewable fuels, drugs and chemicals. De novo enzyme design has generated catalysts for several reactions, but with lower catalytic efficiencies than naturally occurring enzymes. Here we report the use of game-driven crowdsourcing to enhance the activity of a computationally designed enzyme through the functional remodeling of its structure. Players of the online game Foldit were challenged to remodel the backbone of a computationally designed bimolecular Diels-Alderase to enable additional interactions with substrates. Several iterations of design and characterization generated a 24-residue helix-turn-helix motif, including a 13-residue insertion, that increased enzyme activity >18-fold. X-ray crystallography showed that the large insertion adopts a helix-turn-helix structure positioned as in the Foldit model. These results demonstrate that human creativity can extend beyond the macroscopic challenges encountered in everyday life to molecular-scale design problems.
Processes controlling dissolved oxygen and pH in the upper Willamette River basin, Oregon, 1994
Pogue, Ted R.; Anderson, Chauncey W.
1995-01-01
In July and August of 1994, the U. S. Geological Survey in cooperation with the Oregon Department of Environmental Quality (ODEQ) collected data to document the spatial extent and diel variability of dissolved oxygen (DO) concentrations and pH levels in selected reaches of streams in the upper Willamette River Basin. These data were also collected to identify primary factors that control DO concentrations downstream from major point sources as well as to provide ODEQ with data to refine calibration of their steady-state DO and nutrient models for the upper Willamette River Basin. All of the reaches studied had diel variations in DO and pH. The magnitude of the diel variations in DO ranged from 0.2 to 3.9 milligrams per liter (7 to 50 percent-saturation units based on ambient water temperature and barometric pressure) and in pH from 0.3 to 1.4 units. However, of the reaches studied, only the Coast Fork Willamette River from river mile (RM) 21.7 to 12.5 and the Willamette River from RM 151 to 141.6 had field measured violations of State standards for DO and pH. DO concentration and pH in water depend on many factors. Data were collected to examine several major factors, including BOD (biochemical oxygen demand), carbonaceous BOD, nitrogenous BOD, and measures of photosynthetic activity. Of the four study reaches, only a short stretch of the Coast Fork Willamette River has potential for important levels of oxygen consumption from BOD or nitrification. Additionally, water-column primary-productivity measurements indicated that respiration and photosynthesis by free-floating algae did not explain the observed diel variations in DO in the study reaches. Results from a simple mathematical model incorporating measures of community respiration and net primary productivities indicated that periphyton are capable of producing a diel variation of the order of magnitude observed during the August study period. In the Willamette River near Peoria, the combined periphyton DO consumption and production estimate at RM 151 (2.4 mg/L) and RM 144.6 (1.7 mg/L) would account for 90 and 63 percent, respectively, of the observed diel fluctuation. The estimates for the Corvallis reach at RM 132.6 (0.4 mg/L) and RM 130.7 (2.9 mg/L) had a considerably larger range of 36 to 264 percent of DO saturation, respectively. Therefore, because BOD and phytoplankton do not appear to be important contributors to diel DO fluctuations, periphyton are likely the primary contributor to diel fluctuations in the upper Willamette River Basin during July and August.
Modeling Diel Oxygen Dynamics and Ecosystem Metabolism in Weeks Bay, Alabama.
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...
Biogeography of time partitioning in mammals.
Bennie, Jonathan J; Duffy, James P; Inger, Richard; Gaston, Kevin J
2014-09-23
Many animals regulate their activity over a 24-h sleep-wake cycle, concentrating their peak periods of activity to coincide with the hours of daylight, darkness, or twilight, or using different periods of light and darkness in more complex ways. These behavioral differences, which are in themselves functional traits, are associated with suites of physiological and morphological adaptations with implications for the ecological roles of species. The biogeography of diel time partitioning is, however, poorly understood. Here, we document basic biogeographic patterns of time partitioning by mammals and ecologically relevant large-scale patterns of natural variation in "illuminated activity time" constrained by temperature, and we determine how well the first of these are predicted by the second. Although the majority of mammals are nocturnal, the distributions of diurnal and crepuscular species richness are strongly associated with the availability of biologically useful daylight and twilight, respectively. Cathemerality is associated with relatively long hours of daylight and twilight in the northern Holarctic region, whereas the proportion of nocturnal species is highest in arid regions and lowest at extreme high altitudes. Although thermal constraints on activity have been identified as key to the distributions of organisms, constraints due to functional adaptation to the light environment are less well studied. Global patterns in diversity are constrained by the availability of the temporal niche; disruption of these constraints by the spread of artificial lighting and anthropogenic climate change, and the potential effects on time partitioning, are likely to be critical influences on species' future distributions.
Jonsen, Ian D; Myers, Ransom A; James, Michael C
2006-09-01
1. Biological and statistical complexity are features common to most ecological data that hinder our ability to extract meaningful patterns using conventional tools. Recent work on implementing modern statistical methods for analysis of such ecological data has focused primarily on population dynamics but other types of data, such as animal movement pathways obtained from satellite telemetry, can also benefit from the application of modern statistical tools. 2. We develop a robust hierarchical state-space approach for analysis of multiple satellite telemetry pathways obtained via the Argos system. State-space models are time-series methods that allow unobserved states and biological parameters to be estimated from data observed with error. We show that the approach can reveal important patterns in complex, noisy data where conventional methods cannot. 3. Using the largest Atlantic satellite telemetry data set for critically endangered leatherback turtles, we show that the diel pattern in travel rates of these turtles changes over different phases of their migratory cycle. While foraging in northern waters the turtles show similar travel rates during day and night, but on their southward migration to tropical waters travel rates are markedly faster during the day. These patterns are generally consistent with diving data, and may be related to changes in foraging behaviour. Interestingly, individuals that migrate southward to breed generally show higher daytime travel rates than individuals that migrate southward in a non-breeding year. 4. Our approach is extremely flexible and can be applied to many ecological analyses that use complex, sequential data.
Modeling Diel Oxygen Dynamics and Ecosystem Metabolism in a Shallow, Eutrophic Estuary
Weeks Bay is a shallow eutrophic estuary that exhibits frequent summertime diel-cycling hypoxia and periods of dissolved oxygen (DO) oversaturation during the day. Diel DO dynamics in shallow estuaries like Weeks Bay are complex, and may be influenced by wind forcing, vertical an...
The nitrosocarbonyl hetero-Diels-Alder reaction as a useful tool for organic syntheses.
Bodnar, Brian S; Miller, Marvin J
2011-06-14
Organic transformations that result in the formation of multiple covalent bonds within the same reaction are some of the most powerful tools in synthetic organic chemistry. Nitrosocarbonyl hetero-Diels-Alder (HDA) reactions allow for the simultaneous stereospecific introduction of carbon-nitrogen and carbon-oxygen bonds in one synthetic step, and provide direct access to 3,6-dihydro-1,2-oxazines. This Review describes the development of the nitrosocarbonyl HDA reaction and the utility of the resulting oxazine ring in the synthesis of a variety of important, biologically active molecules. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Renault, Kévin; Jouanno, Laurie-Anne; Lizzul-Jurse, Antoine; Renard, Pierre-Yves; Sabot, Cyrille
2016-12-19
Fluorogenic reactions are largely underrepresented in the toolbox of chemoselective ligations despite their tremendous potential, particularly in chemical biology and biochemistry. In this respect, we have investigated in full detail the fluorescence behaviour of the azaphthalamide, a scaffold which is generated through a hetero-Diels-Alder reaction of 5-alkoxyoxazole and maleimide derivatives under mild conditions that are compatible with, among others, peptide chemistry. The scope and limitations of such a fluorogenic labelling strategy were examined through four distinct applications, which target enzymatic activities or bioorthogonal reactions. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Borkin, Dmitry; Morzhina, Elena; Datta, Silpi; Rudnitskaya, Aleksandra; Sood, Abha; Török, Marianna; Török, Béla
2011-03-07
A highly diastereoselective microwave-assisted three component synthesis of azabicyclo[2.2.2]octan-5-ones by a silicotungstic acid-catalyzed aza-Diels-Alder cyclization is described. The one-pot process involves the formation of the in situ generated Schiff base and its immediate cyclization with cyclohex-2-enone. The short reaction times, good yields and excellent diastereoselectivity make this annulation a practical and environmentally attractive method for the synthesis of the target compounds. Preliminary assays were carried out to determine the activity of the products in AChE as well as in amyloid β fibrillogenesis inhibition.
Susanti, Dewi; Liu, Li-Juan; Rao, Weidong; Lin, Sheng; Ma, Dik-Lung; Leung, Chung-Hang; Chan, Philip Wai Hong
2015-06-15
A synthetic method to prepare 3a,6-methanoisoindole esters efficiently by gold(I)-catalyzed tandem 1,2-acyloxy migration/Nazarov cyclization followed by Diels-Alder reaction of 1,4,9-dienyne esters is described. We also report the ability of one example to inhibit binding of tumor necrosis factor-α (TNF-α) to the tumor necrosis factor receptor 1 (TNFR1) site and TNF-α-induced nuclear factor κ-light-chain-enhancer of activated B cells (NF-κB) activation in cell at a half-maximal inhibitory concentration (IC50 ) value of 6.6 μM. Along with this is a study showing the isoindolyl derivative to exhibit low toxicity toward human hepatocellular liver carcinoma (HepG2) cells and its possible mode of activity based on molecular modeling analysis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Rodríguez, Yeray A; Gutiérrez, Margarita; Ramírez, David; Alzate-Morales, Jans; Bernal, Cristian C; Güiza, Fausto M; Romero Bohórquez, Arnold R
2016-10-01
New N-allyl/propargyl 4-substituted 1,2,3,4-tetrahydroquinolines derivatives were efficiently synthesized using acid-catalyzed three components cationic imino Diels-Alder reaction (70-95%). All compounds were tested in vitro as dual acetylcholinesterase and butyryl-cholinesterase inhibitors and their potential binding modes, and affinity, were predicted by molecular docking and binding free energy calculations (∆G) respectively. The compound 4af (IC50 = 72 μm) presented the most effective inhibition against acetylcholinesterase despite its poor selectivity (SI = 2), while the best inhibitory activity on butyryl-cholinesterase was exhibited by compound 4ae (IC50 = 25.58 μm) with considerable selectivity (SI = 0.15). Molecular docking studies indicated that the most active compounds fit in the reported acetylcholinesterase and butyryl-cholinesterase active sites. Moreover, our computational data indicated a high correlation between the calculated ∆G and the experimental activity values in both targets. © 2016 The Authors Chemical Biology & Drug Design Published by John Wiley & Sons Ltd.
Diels-Alder Cycloadditions of Masked o-Benzoquinones with Alkenes.
Georgopanou, Effie; Martini, Katerina-Irene; Pantazis, Panagiotis; Pelagias, Paulos; Voulgari, Penelope; Hadjiarapoglou, Lazaros P
2015-10-02
Diels-Alder cycloadditions of 3-oxobut-1-enyl substituted orthoquinone monoketals with olefinic dienophiles furnished functionalized ortho-endo bicyclo[2.2.2]octenone derivatives with high regio- and stereoselectivities. The competition between self-dimerization and Diels-Alder cycloaddition with an external dienophile usually exists, except in the case of 5-substituted orthoquinone monoketal.
Diel biogeochemical processes and their effect on the aqueous chemistry of streams: A review
Nimick, David A.; Gammons, Christopher H.; Parker, Stephen R.
2011-01-01
This review summarizes biogeochemical processes that operate on diel, or 24-h, time scales in streams and the changes in aqueous chemistry that are associated with these processes. Some biogeochemical processes, such as those producing diel cycles of dissolved O2 and pH, were the first to be studied, whereas processes producing diel concentration cycles of a broader spectrum of chemical species including dissolved gases, dissolved inorganic and organic carbon, trace elements, nutrients, stable isotopes, and suspended particles have received attention only more recently. Diel biogeochemical cycles are interrelated because the cyclical variations produced by one biogeochemical process commonly affect another. Thus, understanding biogeochemical cycling is essential not only for guiding collection and interpretation of water-quality data but also for geochemical and ecological studies of streams. Expanded knowledge of diel biogeochemical cycling will improve understanding of how natural aquatic environments function and thus lead to better predictions of how stream ecosystems might react to changing conditions of contaminant loading, eutrophication, climate change, drought, industrialization, development, and other factors.
NASA Astrophysics Data System (ADS)
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.
Riggs, Alan C.; Striegl, Robert G.; Maestas, Florentino B.; Morganwalp, David W.; Buxton, Herbert T.
1999-01-01
Automated opaque flux-chamber measurements of soil carbon dioxide (CO2) flux (soil respiration) into the atmosphere at the Amargosa Desert Research Site show seasonal and diel cycles of soil respiration that are closely linked with soil temperature and soil moisture. During 1998, soil respiration increased with soil warming through spring, reaching a maximum rate (not counting anomalously high values scattered through the record) of about 0.055 moles CO2 m-2 day-1 around Julian Day 120. Respiration rates then declined along with volumetric soil moisture content, tending to stay at or below about 0.02 moles CO2 per square meter per day (m-2 day -1) for the rest of the year, except after summer rainfalls when respiration sharply increased for short periods. The diel respiration pattern during dry spells is marked by a sharp rise in CO2 flux coincident with steeply rising soil temperatures in the morning, then dropping back to low levels about the time of maximum soil temperature. The reason for this pattern in unclear.
The influence of sea ice, wind speed and marine mammals on Southern Ocean ambient sound
van Opzeeland, Ilse; Boebel, Olaf
2017-01-01
This paper describes the natural variability of ambient sound in the Southern Ocean, an acoustically pristine marine mammal habitat. Over a 3-year period, two autonomous recorders were moored along the Greenwich meridian to collect underwater passive acoustic data. Ambient sound levels were strongly affected by the annual variation of the sea-ice cover, which decouples local wind speed and sound levels during austral winter. With increasing sea-ice concentration, area and thickness, sound levels decreased while the contribution of distant sources increased. Marine mammal sounds formed a substantial part of the overall acoustic environment, comprising calls produced by Antarctic blue whales (Balaenoptera musculus intermedia), fin whales (Balaenoptera physalus), Antarctic minke whales (Balaenoptera bonaerensis) and leopard seals (Hydrurga leptonyx). The combined sound energy of a group or population vocalizing during extended periods contributed species-specific peaks to the ambient sound spectra. The temporal and spatial variation in the contribution of marine mammals to ambient sound suggests annual patterns in migration and behaviour. The Antarctic blue and fin whale contributions were loudest in austral autumn, whereas the Antarctic minke whale contribution was loudest during austral winter and repeatedly showed a diel pattern that coincided with the diel vertical migration of zooplankton. PMID:28280544
Santos, R M; Saggio, A A; Silva, T L R; Negreiros, N F; Rocha, O
2015-01-01
In lentic freshwater ecosystems, patterns of thermal stratification play a considerable part in determining the population dynamics of phytoplankton. In this study we investigated how these thermal patterns and the associated hydrodynamic processes affect the vertical distribution of phytoplankton during two consecutive diel cycles in a warm polymictic urban reservoir in the metropolitan region of São Paulo, Brazil. Water samples were taken and physical, chemical and biological data collected at half-meter intervals of depth along a water column at a fixed site, every 3 hours throughout the 48-hour period. Two events of stratification, followed by deepening of the thermocline occurred during the study period and led to changes in the vertical distribution of phytoplankton populations. Aphanocapsa delicatissima Nägeli was the single dominant species throughout the 48-hour period. In the second diel cycle, the density gradient induced by temperature differences avoided the sedimentation of Mougeotia sp. C. Agardh to the deepest layers. On the other hand, Pseudanabaena galeata Böcher remained in the 4.0-5.5 m deep layer. The thermal structure of the water was directly affected by two meteorological factors: air temperature and wind speed. Changes in the cell density and vertical distribution of the phytoplankton were controlled by the thermal and hydrodynamic events.
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.
Total synthesis of the thiopeptide antibiotic amythiamicin D.
Hughes, Rachael A; Thompson, Stewart P; Alcaraz, Lilian; Moody, Christopher J
2005-11-09
The thiopeptide (or thiostrepton) antibiotics are a class of sulfur containing highly modified cyclic peptides with interesting biological properties, including reported activity against MRSA and malaria. Described herein is the total synthesis of the thiopeptide natural product amythiamicin D, which utilizes a biosynthesis-inspired hetero-Diels-Alder route to the pyridine core of the antibiotic as a key step. Preliminary studies using a range of serine-derived 1-ethoxy-2-azadienes established that hetero-Diels-Alder reaction with N-acetylenamines proceeded efficiently under microwave irradiation to give 2,3,6-trisubstituted pyridines. The thiazole building blocks of the antibiotic were obtained by either classical Hantzsch reactions or by dirhodium(II)-catalyzed chemoselective carbene N-H insertion followed by thionation, and were combined to give the bis-thiazole that forms the left-hand fragment of the antibiotic. The key Diels-Alder reaction of a tris-thiazolyl azadiene with benzyl 2-(1-acetylaminoethenyl)thiazole-4-carboxylate gave the core tetrathiazolyl pyridine, which was elaborated into the natural product by successive incorporation of glycine and bis-thiazole fragments followed by macrocyclization.
Nature's Strategy for Catalyzing Diels-Alder Reaction.
Oikawa, Hideaki
2016-04-21
The enzymes catalyzing a Diels-Alder-type reaction have been attractive targets for organic chemists for years. Recently, Zheng et al. (2016) reported the structure of a formal monofunctional Diels-Alderase PyrI4 complexed with the product and unveiled a detailed catalytic mechanism of a highly important enzyme. Copyright © 2016 Elsevier Ltd. All rights reserved.
Flow velocity and the hydrologic behavior of streams during baseflow.
Steven M. Wondzell; Michael N. Gooseff; Brian L. McGlynn
2007-01-01
Diel variations in stream discharge have long been recognized, but are relatively little studied. Here we demonstrate that these diel fluctuations can be used to investigate both streamflow generation and network routing. We treat evapo-transpiration (ET) as a distributed impulse function in an advection model and analyze the effect of ET on diel fluctuations in...
Montarsi, Fabrizio; Mazzon, Luca; Cazzin, Stefania; Ciocchetta, Silvia; Capelli, Gioia
2015-01-01
The seasonal and daily activity of mosquito vectors of pathogens affecting animals and humans were studied in northeastern Italy at a site within the Po River Delta Park. A CDC-CO2 trap and a gravid trap were operated at 2-h intervals for 24 h every 15 d from May to October 2010. Overall, 5,788 mosquitoes comprising six species were collected, namely Culex pipiens L. (75.1% of total), Aedes caspius (Pallas) (15.2%), Aedes vexans (Meigen) (6.9%), Anopheles maculipennis s.l. Meigen (2.6%), Culiseta annulata (Schrank) (0.2%), and Culex modestus Ficalbi (<0.1%). The relative abundance of these species increased from May until the beginning of July and then decreased, disappearing at the beginning of October. The diel host-seeking patterns and oviposition site-seeking patterns were species specific and were differentially affected by the ecological variables recorded at the day and hour of mosquito collection or two weeks before collection. Knowledge of the seasonal and daily host-seeking patterns of mosquitoes highlights the time periods of the day and the seasons of potential exposure for animals and humans to mosquito-borne pathogens, therefore delineating the best time for the application of preventive measures. Furthermore, knowledge of the oviposition site-seeking activity of the mosquitoes optimizes the capture of gravid females, thereby enhancing the likelihood of detecting pathogens. © The Author 2015. Published by Oxford University Press on behalf of the Entomological Society of America.For Permissions, please e-mail: journals.permissions@oup.com.
Specificity Responses of Grasshoppers in Temperate Grasslands to Diel Asymmetric Warming
Wu, Tingjuan; Hao, Shuguang; Sun, Osbert Jianxin; Kang, Le
2012-01-01
Background Global warming is characterized by not only an increase in the daily mean temperature, but also a diel asymmetric pattern. However, most of the current studies on climate change have only concerned with the mean values of the warming trend. Although many studies have been conducted concerning the responses of insects to climate change, studies that address the issue of diel asymmetric warming under field conditions are not found in the literature. Methodology/Principal Findings We conducted a field climate manipulative experiment and investigated developmental and demographic responses to diel asymmetric warming in three grasshopper species (an early-season species Dasyhippus barbipes, a mid-season species Oedaleus asiaticus, and a late-season species Chorthippus fallax). It was found that warming generally advanced the development of eggs and nymphs, but had no apparent impacts on the hatching rate of eggs, the emergence rate of nymphs and the survival and fecundity of adults in all the three species. Nighttime warming was more effective in advancing egg development than the daytime warming. The emergence time of adults was differentially advanced by warming in the three species; it was advanced by 5.64 days in C. fallax, 3.55 days in O. asiaticus, and 1.96 days in D. barbipes. This phenological advancement was associated with increases in the effective GDDs accumulation. Conclusions/Significance Results in this study indicate that the responses of the three grasshopper species to warming are influenced by several factors, including species traits, developmental stage, and the thermal sensitivity of the species. Moreover, species with diapausing eggs are less responsive to changes in temperature regimes, suggesting that development of diapausing eggs is a protective mechanism in early-season grasshopper for avoiding the risk of pre-winter hatching. Our results highlight the need to consider the complex relationships between climate change and specificity responses of invertebrates. PMID:22848593
Diel variation of selenium and arsenic in a wetland of the Great Salt Lake, Utah
Dicataldo, G.; Johnson, W.P.; Naftz, D.L.; Hayes, D.F.; Moellmer, W.O.; Miller, T.
2011-01-01
Diel (24-h) changes in Se and As concentrations in a freshwater wetland pond bordering the Great Salt Lake (GSL) were examined. Selenium concentrations (filtered and unfiltered) changed on a diel basis, i.e., were depleted during early morning and enriched during daytime over August 17-18. During the May 24-25, 2006 and September 29-30 diel studies, no significant 24-h trends were observed in Se concentrations compared to August, which showed daily maximums up to 59% greater than the daily minimum. Both filtered and unfiltered As concentrations also varied on a diel cycle, with increased concentrations during early morning and decreased concentrations during daytime. Filtered As concentrations increased 110% during the May 24-25, 2006 diel study. Selenium varied in phase with pH, dissolved O2 (DO), and water temperature (Tw) whereas As varied opposite to Se, pH, DO and Tw. Changes in pH, DO and Tw showed a direct linear correlation (r=0.74, 0.75, and 0.55, respectively) to filtered Se. Also pH, DO and Tw were inversely correlated to filtered As concentration (r=-0.88, -0.87, and -0.84, respectively). Equilibrium geochemical speciation and sorption models were used to examine the potential oxidation state changes in Se and As, and sorption and desorption reactions corresponding to the observed 24-h variations in pe and pH. In this wetland it was postulated that diel Se variation was driven by sorption and desorption due to photosynthesis-induced changes in pH and redox conditions. Diel variations of As were hypothesized to be linked to pH-driven sorption and desorption as well as co-precipitation and co-dissolution with mineral phases of Mn. ?? 2010 Elsevier Ltd.
NASA Astrophysics Data System (ADS)
Roe, H. S. J.; Angel, M. V.; Badcock, J.; Domanski, P.; James, P. T.; Pugh, P. R.; Thurston, M. H.
(i) This paper is an introduction to a series of papers describing the diel migrations and interrelationships of a mesopelagic community in the northeast Atlantic. (ii) The biological and physical background to the sampling area is described. (iii) There was little physical structure in the water column to a depth of 1000 m. (iv) The influence of Mediterranean water was detectable at varying depths between 550 and 800 m during the sampling programme. The possibility of mesoscale activity at these depths is discussed. (v) The sampling programme is described. Using the I.O.S. rectangular midwater trawl, the RMT 1 + 8, one hour samples were taken at 4 depth horizons, 100, 250, 450 and 600 m. Each depth was fished continuously for 48 hr. (vi) Additional non-quantitative surface samples, and surface light measurements were made throughout the RMT 1 + 8 sampling period. (vii) 97 hauls were made and the data for fish, decapod Crustacea, mysids, euphausiids, amphipods, copepods, ostracods, siphonophores, medusae, cteniphores and chaetognaths analysed. (viii) General results in terms of total numbers and numbers of species taken by the RMT 1 and the RMT 8 are described. (ix) The populations at 100 and 250 m showed more diel variation than those at 450 and 600 m, but the proportions of individual species and groups changed continuously at all depths. (x) These changes are due to diel vertical migrations. The migrations of most species only involved a part of their populations.
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.
High-Frequency Measurements of Methane Ebullition Over a Growing Season at a Temperate Peatland Site
NASA Technical Reports Server (NTRS)
Goodrich, Jordan P.; Varner, Ruth K.; Frolking, Steve; Duncan, Bryan N.; Crill, Patrick M.
2011-01-01
Bubbles can contribute a significant fraction of methane emissions fr om wetlands; however the range of reported fractions is very large an d accurate characterization of this pathway has proven difficult. Her e we show that continuous automated flux chambers combined with an in tegrated cavity output spectroscopy (ICOS) instrument allow us to qua ntify both CH4 ebullition rate and magnitude. For a temperate poor f en in 2009, ebullition rate varied on hourly to seasonal time scales. A diel pattern in ebullition was identified with peak release occurr ing between 20:00 and 06:00 local time, though steady fluxes (i.e., t hose with a linear increase in chamber headspace CH4 concentration) d id not exhibit diel variability. Seasonal mean ebullition rates peake d at 843.5 +/- 384.2 events m(exp -2)/d during the summer, with a me an magnitude of 0.19 mg CH4 released in each event.
Seasonal changes in partial, reverse diel vertical migrations of cisco Coregonus artedi.
Ahrenstorff, T D; Hrabik, T R
2016-09-01
The objectives of this study were to (1) document changes in partial, reverse diel vertical migrations (DVM) patterns of cisco Coregonus artedi in Ten Mile Lake, MN, U.S.A., throughout the year and (2) evaluate the mechanisms that may cause shifts in migration behaviour. Results indicated that C. artedi vertical distributions remained deep in the water column during the day and night of the spring and autumn, which was related to a low risk, low reward strategy. During summer, a partial migration occurred where a portion of the population remained deeper according to the low risk, low reward strategy, while the other portion performed a more extensive high risk, high reward reverse DVM. In winter, C. artedi did not migrate because there were only low risk, low reward conditions present at all depths. The extensive partial, reverse DVM during summer probably increased the growth potential of C. artedi, helping individuals survive in a lake with low zooplankton prey resources. © 2016 The Fisheries Society of the British Isles.
Martz, Todd R.; Brainard, Russell E.
2012-01-01
Community structure and assembly are determined in part by environmental heterogeneity. While reef-building corals respond negatively to warming (i.e. bleaching events) and ocean acidification (OA), the extent of present-day natural variability in pH on shallow reefs and ecological consequences for benthic assemblages is unknown. We documented high resolution temporal patterns in temperature and pH from three reefs in the central Pacific and examined how these data relate to community development and net accretion rates of early successional benthic organisms. These reefs experienced substantial diel fluctuations in temperature (0.78°C) and pH (>0.2) similar to the magnitude of ‘warming’ and ‘acidification’ expected over the next century. Where daily pH within the benthic boundary layer failed to exceed pelagic climatological seasonal lows, net accretion was slower and fleshy, non-calcifying benthic organisms dominated space. Thus, key aspects of coral reef ecosystem structure and function are presently related to natural diurnal variability in pH. PMID:22952785
Borisova, Kseniya K; Kvyatkovskaya, Elizaveta A; Nikitina, Eugeniya V; Aysin, Rinat R; Novikov, Roman A; Zubkov, Fedor I
2018-04-20
A rare example of chemospecificity in the tandem Diels-Alder reaction of activated alkynes and bis-dienes has been revealed. The reaction between bis-furyl dienes and DMAD occurs at 25-80 °C and leads to kinetically controlled "pincer" adducts, 4a,8a-disubstituted 1,4:5,8-diepoxynaphthalenes. On the contrary, only thermodynamically controlled "domino" adducts (2,3-disubstituted 1,4:5,8-diepoxynaphthalenes) are formed in the same reaction at 140 °C. The "pincer" adducts can be transformed to the "domino" adducts at heating. The rate constants for reactions of both types were calculated using dynamic 1 H NMR spectroscopy.
NASA Astrophysics Data System (ADS)
Putzeys, S.; Yebra, L.; Almeida, C.; Bécognée, P.; Hernández-León, S.
2011-12-01
Studies on carbon active fluxes due to diel migrants are scarce and critical for carbon flux models and biogeochemical estimates. We studied the temporal variability and vertical distribution of biomass, indices of feeding and respiration of the zooplanktonic community north off the Canary Islands during the end of the late winter bloom, in order to assess vertical carbon fluxes in this area. Biomass distribution during the day presented two dense layers of organisms at 0-200 m and around 500 m, whereas at night, most of the biomass concentrated in the epipelagic layer. The gut pigment flux (0.05-0.18 mgC·m - 2 ·d - 1 ) represented 0.22% of the estimated passive export flux (POC flux) while potential ingestion represented 3.91% of the POC (1.24-3.40 mgC·m - 2 ·d - 1 ). The active respiratory flux (0.50-1.36 mgC·m - 2 ·d - 1 ) was only 1.57% of the POC flux. The total carbon flux mediated by diel migrants (respiration plus potential ingestion) ranged between 3.37 and 9.22% of the POC flux; which is three-fold higher than calculating ingestion fluxes from gut pigments. Our results suggest that the fluxes by diel migrants play a small role in the downward flux of carbon in the open ocean during the post-bloom period.
Cross-Diels-Alder reactions of 6-oxo-1-sulfonyl-1,6-dihydropyridine-3-carboxylates.
Teyssot, Marie-Laure; Lormier, Anh-Tuan; Chataigner, Isabelle; Piettre, Serge R
2007-03-30
Electron-poor 6-oxo-1-sulfonyl-1,6-dihydropyridine-3-carboxylates 1b-d undergo cross-Diels-Alder reactions with electron-rich dienes 4a-f under hyperbaric conditions, reacting either as dienophiles to yield normal-electron-demand (NED) cycloadducts 10 and/or 11 or as dienes to give inverse-electron-demand (IED) cycloadducts 12 and/or 13. The latter are converted into 14 and/or 15 through an NED cycloaddition with a second equivalent of electron-rich diene. Acyclic dienes display a propensity to yield NED products, whereas cyclic dienes tend to favor IED cycloadducts. High-pressure activation compares favorably with thermal or microwave activation in terms of both yields and suppression of the transformation of 1 into unreactive pyridines 3. Whereas the Cope rearrangement from IED to NED occurs under thermal conditions, no evidence of its involvement under high pressure could be detected. These and other data point to similar activation energies for the NED and IED processes under these conditions.
Temporal patterns in marine mammal sounds from long-term broadband recordings
NASA Astrophysics Data System (ADS)
Hildebrand, John A.; Wiggins, Sean; Oleson, Erin; Sirovic, Ana; Munger, Lisa; Soldevilla, Melissa; Burtenshaw, Jessica
2005-09-01
Recent advances in the technology for long-term underwater acoustic recording provide new data on the temporal patterns of marine mammal sounds. Autonomous acoustic recordings are now being made with broad frequency bandwidth up to 200-kHz sampling rates. These data allow sound recording from most marine mammal species, including, for instance, the echolocation clicks of odontocetes. Large data storage capacity up to 1280 Gbytes allow these recordings to be conducted over long time periods for study of diel and seasonal calling patterns. Examples will be presented of temporal patterns from long-term recordings collected in four regions: the Bering Sea, offshore southern California, the Gulf of California, and the Southern Ocean. These data provide new insight on marine mammal distribution, seasonality, and behavior.
Atmospheric turbulence triggers pronounced diel pattern in karst carbonate geochemistry
NASA Astrophysics Data System (ADS)
Roland, M.; Serrano-Ortiz, P.; Kowalski, A. S.; Goddéris, Y.; Sánchez-Cañete, E. P.; Ciais, P.; Domingo, F.; Cuezva, S.; Sanchez-Moral, S.; Longdoz, B.; Yakir, D.; Van Grieken, R.; Schott, J.; Cardell, C.; Janssens, I. A.
2013-07-01
CO2 exchange between terrestrial ecosystems and the atmosphere is key to understanding the feedbacks between climate change and the land surface. In regions with carbonaceous parent material, CO2 exchange patterns occur that cannot be explained by biological processes, such as disproportionate outgassing during the daytime or nighttime CO2 uptake during periods when all vegetation is senescent. Neither of these phenomena can be attributed to carbonate weathering reactions, since their CO2 exchange rates are too small. Soil ventilation induced by high atmospheric turbulence is found to explain atypical CO2 exchange between carbonaceous systems and the atmosphere. However, by strongly altering subsurface CO2 concentrations, ventilation can be expected to influence carbonate weathering rates. By imposing ventilation-driven CO2 outgassing in a carbonate weathering model, we show here that carbonate geochemistry is accelerated and does play a surprisingly large role in the observed CO2 exchange pattern of a semi-arid ecosystem. We found that by rapidly depleting soil CO2 during the daytime, ventilation disturbs soil carbonate equilibria and therefore strongly magnifies daytime carbonate precipitation and associated CO2 production. At night, ventilation ceases and the depleted CO2 concentrations increase steadily. Dissolution of carbonate is now enhanced, which consumes CO2 and largely compensates for the enhanced daytime carbonate precipitation. This is why only a relatively small effect on global carbonate weathering rates is to be expected. On the short term, however, ventilation has a drastic effect on synoptic carbonate weathering rates, resulting in a pronounced diel pattern that exacerbates the non-biological behavior of soil-atmosphere CO2 exchanges in dry regions with carbonate soils.
Steven M. Wondzell; Michael N. Gooseff; Brian L. McGlynn
2009-01-01
Diel fluctuations in streamflow during base flow have been observed in many streams and are typically attributed to water losses from evapotranspiration (ET). However, there is no widely transferable conceptual model that explains how ET results in diel fluctuations in streamflow at the watershed outlet. For fluctuations to occur, two factors must be present: (1) some...
Koehler, Kenneth C.; Alge, Daniel L.; Anseth, Kristi S.; Bowman, Christopher N.
2013-01-01
We report a new approach to controlled drug release based upon exploiting the dynamic equilibrium that exists between Diels-Alder reactants and products, demonstrating the release of a furan containing dexamethasone peptide (dex-KGPQG-furan) from a maleimide containing hydrogel. Using a reaction-diffusion model, the release kinetics were tuned to achieve sustained concentrations conducive to osteogenic differentiation of human mesenchymal stem cells (hMSCs). Efficacy was first demonstrated in a 2D culture model, in which dexamethasone release induced significant increases in alkaline phosphatase (ALP) activity and mineral deposition in hMSCs compared to a dexamethasone-free treatment. The results were similar to that observed with a soluble dexamethasone treatment. More dramatic differences were observed in 3D culture, where co-encapsulation of a dexamethasone releasing hydrogel depot within an hMSC-laden extracellular matrix mimetic poly(ethylene glycol) hydrogel resulted in a local and robust osteogenic differentiation. ALP activity reached levels that were up to six times higher than the dexamethasone free treatment. Interestingly, at 5 and 10 day time points, the ALP activity exceeded the dexamethasone positive control, suggesting a potential benefit of sustained release in 3D culture. After 21 days, substantial mineralization comparable to the positive control was also observed in the hydrogels. Collectively, these results demonstrate Diels-Alder modulated release as an effective and versatile new platform for controlled drug delivery that may prove especially beneficial for sustaining the release of low molecular weight molecules in hydrogel systems. PMID:23465826
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.
NASA Astrophysics Data System (ADS)
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 and V descended continuously. Zoeae III had behaviors that were intermediate to those of the earlier- and later-stage zoeae. Postlarvae underwent a normal diel migration (nocturnal ascent) regardless of tides, with the deepest position (below 60 m and/or on the bottom) during the day. These findings give a new perspective towards how complex vertical migration patterns in meroplanktonic larvae enable their retention in inner shelf waters before the final entry of postlarvae into their natal populations.
Buffer capacity, ecosystem feedbacks, and seawater chemistry under global change
NASA Astrophysics Data System (ADS)
Jury, C. P.; Thomas, F. I.; Atkinson, M. J.; Jokiel, P. L.; Onuma, M. A.; Kaku, N.; Toonen, R. J.
2013-12-01
Ocean acidification (OA) results in reduced seawater pH and aragonite saturation state (Ωarag), but also reduced seawater buffer capacity. As buffer capacity decreases, diel variation in seawater chemistry increases. However, a variety of ecosystem feedbacks can modulate changes in both average seawater chemistry and diel seawater chemistry variation. Here we model these effects for a coastal, reef flat ecosystem. We show that an increase in offshore pCO2 and temperature (to 900 μatm and +3°C) can increase diel pH variation by as much as a factor of 2.5 and can increase diel pCO2 variation by a factor of 4.6, depending on ecosystem feedbacks and seawater residence time. Importantly, these effects are different between day and night. With increasing seawater residence time and increasing feedback intensity, daytime seawater chemistry becomes more similar to present-day conditions while nighttime seawater chemistry becomes less similar to present-day conditions. Better constraining ecosystem feedbacks under global change will improve projections of coastal water chemistry, but this study shows the importance of considering changes in both average carbonate chemistry and diel chemistry variation for organisms and ecosystems. Further, we will discuss our recent work examining the effects of diel seawater chemistry variation on coral calcification rates.
Jarrold, Michael D; Humphrey, Craig; McCormick, Mark I; Munday, Philip L
2017-08-31
Elevated CO 2 levels associated with ocean acidification (OA) have been shown to alter behavioural responses in coral reef fishes. However, all studies to date have used stable pCO 2 treatments, not considering the substantial diel pCO 2 variation that occurs in shallow reef habitats. Here, we reared juvenile damselfish, Acanthochromis polyacanthus, and clownfish, Amphiprion percula, at stable and diel cycling pCO 2 treatments in two experiments. As expected, absolute lateralization of A. polyacanthus and response to predator cue of Am. percula were negatively affected in fish reared at stable, elevated pCO 2 in both experiments. However, diel pCO 2 fluctuations reduced the negative effects of OA on behaviour. Importantly, in experiment two, behavioural abnormalities that were present in fish reared at stable 750 µatm CO 2 were largely absent in fish reared at 750 ± 300 µatm CO 2 . Overall, we show that diel pCO 2 cycles can substantially reduce the severity of behavioural abnormalities caused by elevated CO 2 . Thus, past studies may have over-estimated the impacts of OA on the behavioural performance of coral reef fishes. Furthermore, our results suggest that diel pCO 2 cycles will delay the onset of behavioural abnormalities in natural populations.
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.
NASA Astrophysics Data System (ADS)
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.
NASA Astrophysics Data System (ADS)
Harvey, Michel; Galbraith, Peter S.; Descroix, Aurélie
2009-01-01
Vertical distribution of various species and stages of macrozooplankton (euphausiacea, chaetognatha, cnidaria, mysidacea, amphipoda) were determined for different times of the day and related to the physical environment. Stratified sampling with the BIONESS was carried out during seven cruises in spring and fall 1998, 2000, and 2001, and fall 1999, in two different habitats in the St. Lawrence marine system: the lower St. Lawrence Estuary and the NW Gulf of St. Lawrence. Our results indicate that the various macrozooplankton species were distributed throughout the whole water column including the surface layer, the cold intermediate layer (CIL), and the deep layer at different times of day and night in both areas during all periods. Moreover, three types of migrational patterns were observed within this zooplanktonic community: (1) nocturnal ascent by the whole population, (2) segregation into two groups; one which performed nocturnal accent and another which remained in the deep, and (3) no detectable migration. We also observed that the diel vertical migration (DVM) amplitude in most of the macrozooplankton species varied as a function of physical factors, in particular the spatio-temporal variations of the CIL thermal properties, including the upper and the lower limits of the CIL and the depth of the CIL core temperature. Finally, the different DVM patterns coupled with estuarine circulation patterns and bottom topography could place animals in different flow regimes by night and by day and contribute to their retention (aggregation) and/or dispersion in different areas, time of the day, and seasons.
Saha, C K; Ammon, C; Berg, W; Fiedler, M; Loebsin, C; Sanftleben, P; Brunsch, R; Amon, T
2014-01-15
Understanding seasonal and diel variations of ammonia (NH3) and methane (CH4) emissions from a naturally ventilated dairy (NVD) building may lead to develop successful control strategies for reducing emissions throughout the year. The main objective of this study was to quantify seasonal and diel variations of NH3 and CH4 emissions together with associated factors influencing emissions. Measurements were carried out with identical experimental set-up to cover three winter, spring and summer seasons, and two autumn seasons in the years 2010, 2011, and 2012. The data from 2010 and 2011 were used for developing emission prediction models and the data from 2012 were used for model validation. The results showed that NH3 emission varied seasonally following outside temperature whereas CH4 emission did not show clear seasonal trend. Diel variation of CH4 emission was less pronounced than NH3. The average NH3 and CH4 emissions between 6a.m. and 6p.m. were 66% and 33% higher than the average NH3 and CH4 emissions between 6p.m. and 6a.m., respectively for all seasons. The significant relationships (P<0.0001) between NH3 and influencing factors were found including outside temperature, humidity, wind speed and direction, hour of the day and day of the year. The significant effect (P<0.0001) of climate factors, hours of the day and days of the year on CH4 emission might be directly related to activities of the cows. © 2013.
Diels-Alder addition to H2O@C60 an electronic and structural study
NASA Astrophysics Data System (ADS)
Reveles, J. Ulises; Govinda, K. C.; Baruah, Tunna; Zope, Rajendra R.
2017-10-01
Exohedral reactivity of endohedral fullerenes has aroused a significant interest because of its potential applications. The present letter examines the effect of an entrapped single water molecule on the reactivity of C60. We study the thermodynamics and kinetics of a Diels-Alder reaction occurring at all non-identical bonds of free C60 and H2O@C60. Our calculations show that encapsulation of water does not have a significant effect on H2O@C60 reactivity compared to C60, as attested by the investigation of the reaction under several orientations of H2O inside C60. Reaction and activation energies indicate that [6,6] bonds are the most reactive sites.
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.
NASA Astrophysics Data System (ADS)
Bachand, P.; Bachand, S. M.; Fleck, J.; Anderson, F.
2011-12-01
Hydrology arguably plays the most important role in biogeochemical cycling of mercury in wetlands and other shallow aquatic systems. CFSTR, PFR and non-ideal reactor models are oftentimes currently used to hydrologically assess these systems and to account for the fate, transport and cycling of constituents of concern (COC) with systems assumed to be non-leaky and with diffusion dominating soil transport. Yet a number of results in the literature imply transpiration drives soil transport: transpiration into the root zone is in the range of 50 - 75% of ET seasonally; gaseous emissions from aquatic systems show a diel pattern that tracks diel ET patterns; in long detention time aquatic systems ET is the largest sink for applied surface waters; and non-reactive tracers when applied to surface waters can find themselves in the root zone and within plants. All these findings strongly suggest transpiration driven infiltration into the root zone, is a significant hydrologic pathway for constituents and is an important transport mechanism. This paper examines the annual water budget for four shallow aquatic land uses in the Yolo Bypass, California: rice, wild rice, fallowed fields and wetlands. Results indicate that differences in hydrology between the fields, particularly the temporal nature of transpiration, play a significant role in mercury transformations and transport. During the irrigation period, fallowed fields discharged 6 cm of surface water (15% applied water), rice fields 31 - 43 cm (27 - 31% applied water), and wild rice fields 16 - 39 cm (15 - 31% applied water). Evapotranspiration rates were in the range of 120 - 130 cm/y for all land uses (i.e. rice, wild rice, fallowed fields and seasonal wetlands) except for the permanent wetland which was about 1/3 higher at about 170 cm/y. During the summer, approximately 50% of the applied surface water was drawn into the root zone to meet transpiration demands. Based upon results from our water budget and utilizing modified Peclet No. calculations, we quantified the relative importance of upward diffusion from the sediments and downward advection from transpiration as hydrologic transport mechanisms in the root zone. Transpiration driven infiltration moves water past the diffusive zone within 1 - 2 days in this system during the summer months. With the waning seasons, evapotranspiration diminishes until by winter diffusion dominates throughout the entire root zone. This model has great implications on the analyses of soil biogeochemical process in the root zone of shallow aquatic systems. Downward advection is a major transport mechanism into the root zone of shallow flooded aquatic systems and provides an important physical mechanism that drives variability in the seasonal and diel storage; release and cycling of COCs; and the creation of both a physical and chemical barrierd to upward diffusion of soil-borne COCs into the water column. Models that do not account for root zone interactions may not be able to capture diel and seasonal differences. Moreover, these interactions may lead to unanticipated environmental consequences as a result of cultural practices.
NASA Astrophysics Data System (ADS)
Jarvis, S. K.; Harmon, R. E.; Barnard, H. R.; Randall, J.; Singha, K.
2017-12-01
The critical zone (CZ)—an open system extending from canopy top to the base of groundwater—is a highly dynamic and heterogeneous environment. In forested terrain, trees make up a large component of the CZ. This work aims to quantify the connection between vegetation and subsurface water storage at a hillslope scale within a forested watershed in the H.J. Andrews Experimental Forest, Oregon. To identify the mechanism(s) controlling the connection at the hillslope scale, we observe patterns in electrical conductivity using 2D-time lapse-DC resistivity. To compare inversions through time a representative error model was determined using L-curve criterion. Inverted data show high spatial variability in ground electrical conductivity and variation at both diel and seasonal timescales. These changes are most pronounced in areas corresponding to dense vegetation. The diel pattern in electrical conductivity is also observed in monitored sap flow sensors, water-level gauges, tensiometers, and sediment thermal probes. To quantify the temporal connection between these data over the course of the growing season a cross correlation analysis was conducted. Preliminary data show that over the course of the growing season transpiration becomes decoupled from both groundwater and soil moisture. Further decomposition of the inverted time lapse data will highlight spatial variability in electrical conductivity providing insight into the where, when, and how(s) of tree-modified subsurface storage.
Arctic complexity: a case study on diel vertical migration of zooplankton
Berge, Jørgen; Cottier, Finlo; Varpe, Øystein; Renaud, Paul E.; Falk-Petersen, Stig; Kwasniewski, Sawomir; Griffiths, Colin; Søreide, Janne E.; Johnsen, Geir; Aubert, Anais; Bjærke, Oda; Hovinen, Johanna; Jung-Madsen, Signe; Tveit, Martha; Majaneva, Sanna
2014-01-01
Diel vertical migration (DVM) of zooplankton is a global phenomenon, characteristic of both marine and limnic environments. At high latitudes, patterns of DVM have been documented, but rather little knowledge exists regarding which species perform this ecologically important behaviour. Also, in the Arctic, the vertically migrating components of the zooplankton community are usually regarded as a single sound scattering layer (SSL) performing synchronized patterns of migration directly controlled by ambient light. Here, we present evidence for hitherto unknown complexity of Arctic marine systems, where zooplankton form multiple aggregations through the water column seen via acoustics as distinct SSLs. We show that while the initiation of DVM during the autumnal equinox is light mediated, the vertical positioning of the migrants during day is linked more to the thermal characteristics of water masses than to irradiance. During night, phytoplankton biomass is shown to be the most important factor determining the vertical positioning of all migrating taxa. Further, we develop a novel way of representing acoustic data in the form of a Sound Image (SI) that enables a direct comparison of the relative importance of each potential scatterer based upon the theoretical contribution of their backscatter. Based on our comparison of locations with contrasting hydrography, we conclude that a continued warming of the Arctic is likely to result in more complex ecotones across the Arctic marine system. PMID:25221372
Theoretical study of the Diels-Alder reaction between o-benzoquinone and norbornadiene
NASA Astrophysics Data System (ADS)
Quijano-Quiñones, Ramiro F.; Quesadas-Rojas, M.; Cuevas, Gabriel; Mena-Rejón, Gonzalo J.
2013-06-01
The reaction between norbornadiene and o-benzoquinone is an important step in polyalicyclic rigid structures synthesis. It has been considered that this reaction is an example of Diels-Alder (DA) and hetero-Diels-Alder (HDA) cycloadditions with o-benzoquinone acting as diene (forming C-C bonds) and heterodiene (forming O-C bonds). We have performed a Density Functional Theory study of this reaction, employing B3LYP, mPW1PW91, and B1B95 functionals and 6-31G(d,p) and 6-31+G(d,p) Gaussian type basis sets. The results indicate that Diels-Alder is a feasible mechanism for both reactions, but should not be the main route to the formation of products with C-C bonds.
Bu, Hongliang; Wang, Fang; McShea, William J; Lu, Zhi; Wang, Dajun; Li, Sheng
2016-01-01
Understanding the interactions between species and their coexistence mechanisms will help explain biodiversity maintenance and enable managers to make sound conservation decisions. Mesocarnivores are abundant and diverse mid-sized carnivores and can have profound impacts on the function, structure and dynamics of ecosystem after the extirpation of apex predators in many ecosystems. The moist temperate forests of Southwest China harbor a diverse community of mesocarnivores in the absence of apex predators. Sympatric species tend to partition limited resources along time, diet and space to facilitate coexistence. We determined the spatial and temporal patterns for five species of mesocarnivores. We used detection histories from a large camera-trap dataset collected from 2004-2015 with an extensive effort of 23,313 camera-days from 495 camera locations. The five mesocarnivore species included masked palm civet Paguma larvata, leopard cat Prionailurus bengalensis, hog badger Arctonyx collaris, yellow-throated marten Martes flavigula, and Siberian weasel Mustela sibirica. Only the masked palm civet and hog badger tended to avoid each other; while for other pairs of species, they occurred independently of each other, or no clear pattern observed. With regard to seasonal activity, yellow-throated marten was most active in winter, opposite the pattern observed for masked palm civet, leopard cat and hog badger. For diel activity, masked palm civet, leopard cat and hog badger were primarily nocturnal and crepuscular; yellow-throated marten was diurnal, and Siberian weasel had no clear pattern for most of the year (March to November), but was nocturnal in the winter (December to February). The seasonal shift of the Siberian weasel may be due to the high diet overlap among species in winter. Our results provided new facts and insights into this unique community of mesocarnivores of southwest China, and will facilitate future studies on the mechanism determining coexistence of animal species within complex system.
Wencewicz, Timothy A; Yang, Baiyuan; Rudloff, James R; Oliver, Allen G; Miller, Marvin J
2011-10-13
The discovery, syntheses, and structure-activity relationships (SAR) of a new family of heterocyclic antibacterial compounds based on N-alkyl-N-(pyridin-2-yl)hydroxylamine scaffolds are described. A structurally diverse library of ∼100 heterocyclic molecules generated from Lewis acid-mediated nucleophilic ring-opening reactions with nitroso Diels-Alder cycloadducts and nitroso ene reactions with substituted alkenes was evaluated in whole cell antibacterial assays. Compounds containing the N-alkyl-N-(pyridin-2-yl)hydroxylamine structure demonstrated selective and potent antibacterial activity against the Gram-positive bacterium Micrococcus luteus ATCC 10240 (MIC(90) = 2.0 μM or 0.41 μg/mL) and moderate activity against other Gram-positive strains including antibiotic resistant strains of Staphylococcus aureus (MRSA) and Enterococcus faecalis (VRE). A new synthetic route to the active core was developed using palladium-catalyzed Buchwald-Hartwig amination reactions of N-alkyl-O-(4-methoxybenzyl)hydroxylamines with 2-halo-pyridines that facilitated SAR studies and revealed the simplest active structural fragment. This work shows the value of using a combination of diversity-oriented synthesis (DOS) and parallel synthesis for identifying new antibacterial scaffolds.
Wencewicz, Timothy A.; Yang, Baiyuan; Rudloff, James R.; Oliver, Allen G.; Miller, Marvin J.
2011-01-01
The discovery, syntheses, and structure-activity relationships (SAR) of a new family of heterocyclic antibacterial compounds based on N-alkyl-N-(pyridin-2-yl)hydroxylamine scaffolds are described. A structurally diverse library of ~100 heterocyclic molecules generated from Lewis acid-mediated nucleophilic ring opening reactions with nitroso Diels-Alder cycloadducts and nitroso ene reactions with substituted alkenes was evaluated in whole cell antibacterial assays. Compounds containing the N-alkyl-N-(pyridin-2-yl)hydroxylamine structure demonstrated selective and potent antibacterial activity against the Gram-positive bacterium Micrococcus luteus ATCC 10240 (MIC90 = 2.0 μM or 0.41 μg/mL) and moderate activity against other Gram-positive strains including antibiotic resistant strains of Staphylococcus aureus (MRSA) and Enterococcus faecalis (VRE). A new synthetic route to the active core was developed using palladium-catalyzed Buchwald-Hartwig amination reactions of N-alkyl-O-(4-methoxybenzyl)hydroxylamines with 2-halo-pyridines that facilitated SAR studies and revealed the simplest active structural fragment. This work shows the value of using a combination of diversity-oriented synthesis (DOS) and parallel synthesis for identifying new antibacterial scaffolds. PMID:21859126
NASA Astrophysics Data System (ADS)
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.
Burns, S. P.; Blanken, P. D.; Turnipseed, A. A.; ...
2015-12-15
Precipitation changes the physical and biological characteristics of an ecosystem. Using a precipitation-based conditional sampling technique and a 14 year data set from a 25 m micrometeorological tower in a high-elevation subalpine forest, we examined how warm-season precipitation affected the above-canopy diel cycle of wind and turbulence, net radiation R net, ecosystem eddy covariance fluxes (sensible heat H, latent heat LE, and CO 2 net ecosystem exchange NEE) and vertical profiles of scalars (air temperature T a, specific humidity q, and CO 2 dry mole fraction χ c). This analysis allowed us to examine how precipitation modified these variables frommore » hourly (i.e., the diel cycle) to multi-day time-scales (i.e., typical of a weather-system frontal passage). During mid-day we found the following: (i) even though precipitation caused mean changes on the order of 50–70 % to R net, H, and LE, the surface energy balance (SEB) was relatively insensitive to precipitation with mid-day closure values ranging between 90 and 110 %, and (ii) compared to a typical dry day, a day following a rainy day was characterized by increased ecosystem uptake of CO 2 (NEE increased by ≈ 10 %), enhanced evaporative cooling (mid-day LE increased by ≈ 30 W m –2), and a smaller amount of sensible heat transfer (mid-day H decreased by ≈ 70 W m –2). Based on the mean diel cycle, the evaporative contribution to total evapotranspiration was, on average, around 6 % in dry conditions and between 15 and 25 % in partially wet conditions. Furthermore, increased LE lasted at least 18 h following a rain event. At night, even though precipitation (and accompanying clouds) reduced the magnitude of R net, LE increased from ≈ 10 to over 20 W m –2 due to increased evaporation. Any effect of precipitation on the nocturnal SEB closure and NEE was overshadowed by atmospheric phenomena such as horizontal advection and decoupling that create measurement difficulties. Above-canopy mean χ c during wet conditions was found to be about 2–3 μmol mol –1 larger than χ c on dry days. This difference was fairly constant over the full diel cycle suggesting that it was due to synoptic weather patterns (different air masses and/or effects of barometric pressure). Lastly, the effect of clouds on the timing and magnitude of daytime ecosystem fluxes is described.« less
Espeleta, Javier F.; Cardon, Zoe G.; Mayer, K. Ulrich; ...
2016-11-12
Hydro-biogeochemical processes in the rhizosphere regulate nutrient and water availability, and thus ecosystem productivity. We hypothesized that two such processes often neglected in rhizosphere models — diel plant water use and competitive cation exchange — could interact to enhance availability of K + and NH 4 +, both high-demand nutrients. A rhizosphere model with competitive cation exchange was used to investigate how diel plant water use (i.e., daytime transpiration coupled with no nighttime water use, with nighttime root water release, and with nighttime transpiration) affects competitive ion interactions and availability of K + and NH 4 +. Competitive cation exchangemore » enabled lowdemand cations that accumulate against roots (Ca 2+, Mg 2+, Na +) to desorb NH 4 + and K + from soil, generating non-monotonic dissolved concentration profiles (i.e. ‘hotspots’ 0.1–1 cm from the root). Cation accumulation and competitive desorption increased with net root water uptake. Daytime transpiration rate controlled diel variation in NH 4 + and K + aqueous mass, nighttime water use controlled spatial locations of ‘hotspots’, and day-to-night differences in water use controlled diel differences in ‘hotspot’ concentrations. Finally, diel plant water use and competitive cation exchange enhanced NH 4 + and K + availability and influenced rhizosphere concentration dynamics. Demonstrated responses have implications for understanding rhizosphere nutrient cycling and plant nutrient uptake.« less
Winter diel habitat use and movement by subadult bull trout in the upper Flathead River, Montana
Muhlfeld, Clint C.; Glutting, Steve; Hunt, Rick; Daniels, Durae; Marotz, Brian
2003-01-01
We evaluated the diel habitat use and movement of subadult bull trout Salvelinus confluentus by use of radiotelemetry during winter in the upper Flathead River, Montana. Of the 13 monitored bull trout, 12 (92%) made at least one diel movement to other habitat locations during their respective day–night tracking surveys and moved an average of 73% of the time. The median distance moved from day to night locations by the mobile fish was 86 m (range, 27–594 m). Diel shifts in habitat use by nine of the tagged fish were related to light intensity; nocturnal emergence generally commenced immediately after the onset of night, and daytime concealment occurred at daybreak. When diel shifts in microhabitat use occurred, subadult bull trout moved from deep, midchannel areas during the day to shallow, low-velocity areas along the channel margins without overhead cover at night. Resource managers who wish to protect the overwintering habitat features preferred by subadult bull trout in the upper Flathead River should use natural flow management strategies that maximize and stabilize channel margin habitats at night.
NASA Astrophysics Data System (ADS)
Salavati-fard, Taha; Caratzoulas, Stavros; Doren, Douglas J.
2017-03-01
Dehydration of the cycloadduct produced from the Diels-Alder reaction between 2,5-dimethylfuran and maleic anhydride to 3,6-dimethylphthalic anhydride exemplifies an important step in producing platform chemicals from biomass. The mechanisms of dehydration and catalytic effects of Lewis and Brønsted acids are investigated with density functional theory. The uncatalyzed reaction has a very high activation barrier (68.7 kcal/mol) in the gas phase and it is not significantly affected by solvation. With a Lewis acid catalyst, modeled as an alkali ion, the activation barriers are reduced, but intermediates are also stabilized. The net effect in vacuum is that the energetic span, or apparent activation energy of the catalytic cycle, is 77.9 kcal/mol, even higher than the barrier in the uncatalyzed case. In solution, however, the energetic span is reduced by as much as 20 kcal/mol, due to differences in the solvation energy of the transition states and intermediates. In the case of a Brønsted acid catalyst, modeled as a proton, the gas phase transition state energies are reduced even more than in the Lewis acid case, and there is no strong stabilization of the intermediates. The energetic span in vacuum is only 13.8 kcal/mol and is reduced even further in solution. Brønsted acid catalysis appears to be the preferred mechanism for dehydration of this cycloadduct. Since the Diels-Alder reaction that produced the molecule has previously been shown to be catalyzed by Brønsted acids, this suggests that a single catalyst could be used to accelerate both steps.
Hajbi, Youssef; Neagoie, Cléopatra; Biannic, Bérenger; Chilloux, Aurélie; Vedrenne, Emeline; Baldeyrou, Brigitte; Bailly, Christian; Mérour, Jean-Yves; Rosca, Sorin; Routier, Sylvain; Lansiaux, Amélie
2010-11-01
New 1,5-dihydro-4-(substituted phenyl)-3H-furo[3,4-b]carbazol-3-ones were synthesised via a key step Diels-Alder reaction under microwave irradiation. 3-Formylindole was successfully used in a 6-step synthesis to obtain those complex heterocycles. The Diels-Alder reaction generating the carbazole ring was optimised under thermal conditions or microwave irradiation. After cleavage of functional groups, DNA binding, topoisomerase inhibition and cytotoxic properties of the new-formed furocarbazoles were investigated. These carbazoles do not present a strong interaction with the DNA, and do not modify the relaxation of the DNA in the presence of topoisomerase I or II except for one promising compound. This compound is a potent topoisomerase II inhibitor, and its cellular activity is not moderated compared to etoposide. The synthesis of these molecules allowed the generalisation of the method using indole and 5-OBn indole and several benzaldehydes. The synthesis of these molecules produced chemical structures endowed with promising cytotoxic and topoisomerase II inhibition activities. Copyright © 2010 Elsevier Masson SAS. All rights reserved.
Chow, Chun P; Shea, Kenneth J
2005-03-23
The chiral ruthenium salen complex, 13b, functions as an efficient catalyst for the sequential oxidation and asymmetric Diels-Alder cycloaddition of hydroxamic acids and N-hydroxy formate esters. This result provides evidence for the formation of a ruthenium-nitroso formate (acyl nitroso) intermediate. The Diels-Alder precursors are prepared from simple building blocks, and the cycloadducts, bridged oxazinolactams, can serve as useful intermediates in organic synthesis.
Fine Scale Baleen Whale Behavior Observed via Tagging Over Daily Time Scales
2012-09-30
right whales and sei whales) and the diel vertical migration behavior of their copepod prey. I hypothesize that (1) right whales track the diel...vertical migration of copepods by feeding near the bottom during the day and at the surface at night, and (2) sei whales are unable to feed on copepods at...depth during the day, and are therefore restricted to feeding on copepods at the surface only. Because copepod diel vertical migration is variable
Fine Scale Baleen Whale Behavior Observed via Tagging Over Daily Time Scales
2013-09-30
sei whales) and the diel vertical migration behavior of their copepod prey. I hypothesize that (1) right whales track the diel vertical migration of... copepods by feeding near the bottom during the day and at the surface at night, and (2) sei whales are unable to feed on copepods at depth during the...day, and are therefore restricted to feeding on copepods at the surface only. Because copepod diel vertical migration is variable over time (days to
Natural Diels-Alderases: Elusive and Irresistable
Klas, Kimberly; Tsukamoto, Sachiko; Sherman, David H.; Williams, Robert M.
2016-01-01
Eight examples of biosynthetic pathways wherein a natural enzyme has been identified and claimed to function as a catalyst for the [4+2] cycloaddition reaction, namely, Diels-Alderases, are briefly reviewed. These are discussed in the context of the mechanistic challenges associated with the technical difficulty of proving that the net formal [4+2] cycloaddition under study, indeed proceeds through a synchronous, mechanism and that the putative biosynthetic enzyme deploys the pericyclic transition state required for a Diels-Alder cycloaddition reaction. PMID:26495876
Using Bio-Optics to Reveal Phytoplankton Physiology from a Wirewalker Autonomous Platform
NASA Technical Reports Server (NTRS)
Omand, M. M.; Cetinic, I.; Lucas, A. J.
2017-01-01
Rapid, wave-powered profiling of bio-optical properties from an autonomous Wirewalker platform provides useful insights into phytoplankton physiology, including the patterns of diel growth, phytoplankton mortality, nonphotochemical quenching of chlorophyll a fluorescence, and natural (sun-induced) fluorescence of mixed communities. Methods are proposed to quantify each of these processes. Such autonomous measurements of phytoplankton physiological rates and responses open up new possibilities for studying phytoplankton in situ, over longer periods, and under a broader range of environmental conditions.
A Diels-Alder Route to Angularly Functionalized Bicyclic Structures
Kim, Woo Han; Lee, Jun Hee; Aussedat, Baptiste; Danishefsky, Samuel J.
2010-01-01
A Diels-Alder based route to trans-fused angularly functionalized bicyclic structures has been developed. This transformation features the use of a tetrasubstituted dienophile in the cycloaddition step. PMID:20717474
Photo-Induced Click Chemistry for DNA Surface Structuring by Direct Laser Writing.
Kerbs, Antonina; Mueller, Patrick; Kaupp, Michael; Ahmed, Ishtiaq; Quick, Alexander S; Abt, Doris; Wegener, Martin; Niemeyer, Christof M; Barner-Kowollik, Christopher; Fruk, Ljiljana
2017-04-11
Oligonucleotides containing photo-caged dienes were prepared and shown to react quantitatively in a light-induced Diels-Alder cycloaddition with functional maleimides in aqueous solution within minutes. Due to its high yield and fast rate, the reaction was exploited for DNA surface patterning with sub-micrometer resolution employing direct laser writing (DLW). Functional DNA arrays were written by direct laser writing (DLW) in variable patterns, which were further encoded with fluorophores and proteins through DNA directed immobilization. This mild and efficient light-driven platform technology holds promise for the fabrication of complex bioarrays with sub-micron resolution. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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 enough to spawn. Given the interannual variation in the timing and intensity of predation pressure, the advantages of a particular movement strategy will likely vary among years. Regardless, movements by salmon allowed individuals to exploit fine-scale habitat heterogeneity during reproduction, which appears to be a strategy to reduce predation risk on the spawning grounds. © 2014 The Authors. Journal of Animal Ecology © 2014 British Ecological Society.
Oviposition of aquatic insects in a tropical high altitude stream.
Rios-Touma, Blanca; Encalada, A C; Prat, N
2012-12-01
The persistence of aquatic insect populations in streams depends on the recruitment of larval populations from egg masses deposited by adults, especially after disturbance. However, recruitment of aquatic populations by oviposition is a process that remains unstudied in streams and rivers. The objectives of our study were to document flying and oviposition patterns of aquatic insects in a high altitude tropical stream during both dry and wet seasons. In particular we studied 1) richness and abundance of adult forms of aquatic insects flying and ovipositing; 2) number of eggs (oviposition pattern), egg mass identity, and morphology; and 3) substrate preferences by ovipositing females. We found 2,383 aquatic insects corresponding to 28 families, with dipterans representing 89% of total individuals collected. Adult insects had lower richness (28 taxa) than larval diversity (up to 52 taxa) and distinct community composition. Richness and relative abundance of most taxa (adults) were not significantly different between seasons, behaviors, diel period, or all three. During both sampling periods we found females with eggs in a total of 15 different families (13 in the dry season and 14 in the wet season). There were no significant differences in the proportion of females with eggs between seasons, diel periods, or different behaviors (flying versus ovipositing traps) of the different female taxa. Few types of egg masses were found in rocks at the stream during both seasons, and most egg masses found corresponded to families Baetidae and Chironomidae. Finally, we provide the first description of eggs masses (size, shape, color, and number of eggs per female) of gravid females (10 taxa) and those found in the stream substrate (six taxa) of Andean macroinvertebrates. This is the first study reporting oviposition, adult diversity, and oviposition patterns of aquatic insects in the Andean region.
Food resource effects on diel movements and body size of cisco in north-temperate lakes.
Ahrenstorff, Tyler D; Hrabik, Thomas R; Jacobson, Peter C; Pereira, Donald L
2013-12-01
The movement patterns and body size of fishes are influenced by a host of physical and biological conditions, including temperature and oxygen, prey densities and foraging potential, growth optimization, and predation risk. Our objectives were to (1) investigate variability in vertical movement patterns of cisco (Coregonus artedi) in a variety of inland lakes using hydroacoustics, (2) explore the causal mechanisms influencing movements through the use of temperature/oxygen, foraging, growth, and predation risk models, and (3) examine factors that may contribute to variations in cisco body size by considering all available information. Our results show that cisco vertical movements vary substantially, with different populations performing normal diel vertical migrations (DVM), no DVM, and reverse DVM in lakes throughout Minnesota and northern Wisconsin, USA. Cisco populations with the smallest body size were found in lakes with lower zooplankton densities. These smaller fish showed movements to areas of highest foraging or growth potential during the day and night, despite moving out of preferred temperature and oxygen conditions and into areas of highest predation risk. In lakes with higher zooplankton densities, cisco grew larger and had movements more consistent with behavioral thermoregulation and predator avoidance, while remaining in areas with less than maximum foraging and growth potential. Furthermore, the composition of potential prey items present in each lake was also important. Cisco that performed reverse DVM consumed mostly copepods and cladocerans, while cisco that exhibited normal DVM or no migration consumed proportionally more macro-zooplankton species. Overall, our results show previously undocumented variation in migration patterns of a fish species, the mechanisms underlying those movements, and the potential impact on their growth potential.
Ahrenstorff, Tyler D.; Hrabik, Thomas R.; Stockwell, Jason D.; Yule, Daniel L.; Sass, Greg G.
2011-01-01
Diel vertical migrations are common among many aquatic species and are often associated with changing light levels. The underlying mechanisms are generally attributed to optimizing foraging efficiency or growth rates and avoiding predation risk (μ). The objectives of this study were to (1) assess seasonal and interannual changes in vertical migration patterns of three trophic levels in the Lake Superior pelagic food web and (2) examine the mechanisms underlying the observed variability by using models of foraging, growth, and μ. Our results suggest that the opossum shrimp Mysis diluviana, kiyi Coregonus kiyi, and siscowet lake trout Salvelinus namaycush migrate concurrently during each season, but spring migrations are less extensive than summer and fall migrations. In comparison with M. diluviana, kiyis, and siscowets, the migrations by ciscoes C. artedi were not as deep in the water column during the day, regardless of season. Foraging potential and μ probably drive the movement patterns of M. diluviana, while our modeling results indicate that movements by kiyis and ciscoes are related to foraging opportunity and growth potential and receive a lesser influence from μ. The siscowet is an abundant apex predator in the pelagia of Lake Superior and probably undertakes vertical migrations in the water column to optimize foraging efficiency and growth. The concurrent vertical movement patterns of most species are likely to facilitate nutrient transport in this exceedingly oligotrophic ecosystem, and they demonstrate strong linkages between predators and prey. Fishery management strategies should use an ecosystem approach and should consider how altering the densities of long-lived top predators produces cascading effects on the nutrient cycling and energy flow in lower trophic levels.
Diel and Seasonal Activities of Culicoides spp. near Yankeetown, Florida.
1985-01-01
immature stages. J. Med. Entomol. 9: 51-59. Lee, V.H. 1968. Parthenogenesis and autogeny in Culicoides bambusicola Lutz (Ceratopogonidae, Diptera). J...method for the isolation of fresh-water invertebrates from soil samples. Ecology 41: 573-574. Williams, R.W. 1961. Parthenogenesis and autogeny in
Kuwabara, James S.
1992-01-01
Diel relationships between physical and chemical parameters and biomass were examined along a 57-km reach of Whitewood Creek, South Dakota, between 29 August and 2 September 1988. A time lag of ∼3-6 h for fluctuations in soluble reactive phosphorus (SRP) concentrations (ranging from 0.1 to 0.5 μM at the downstream sites) relative to dissolved arsenic (ranging from 0.3 to 1.2 μM as arsenate (pentavalent arsenic)) was consistent with our laboratory studies (reported elsewhere) showing preferential cell sorption of orthophosphate over arsenate by creek periphyton. The potential biological effects on SRP diel fluctuations contrasts with abiotic sorption controls for dissolved arsenate (a chemically similar anion). Cycles for pH, like water temperature cycles, lagged irradiance cycles by 1-3 h. Like pH, the amplitude of dissolved arsenic diel cycles was greatest at the site with most abundant biomass. Diel fluctuations in specific conductance (an indicator of groundwater inputs at elevated conductivity relative to the water column) were out of phase with both SRP and dissolved arsenic concentrations suggesting that groundwater was not the direct source of these solutes.
NASA Astrophysics Data System (ADS)
Fei, Jie; Duan, Xiao; Luo, Lan; Zhang, Chao; Qi, Ying; Li, Hejun; Feng, Yongqiang; Huang, Jianfeng
2018-03-01
Carbon fibers (CFs) were grafted with methyl acrylic via Diels-Alder reaction at the different oil bath temperature effectively creating a carboxyl functionalized surface. The effect of grafting temperature on the surface morphology and functional groups of carbon fibers were investigated by FTIR, Raman spectroscopy, XPS and SEM respectively. The results showed that the optimal grafting temperature was 80 °C, and the relative surface coverage by carboxylic acid groups increased from an initial 5.16% up to 19.30% significantly improved the chemical activity without damaging the skin and core region of the carbon fibers. Mechanical property tests indicated that the shear and tensile strength of the sample with the grafting temperature of 80 °C (CFRP-3) increased obviously by 90.3% and 78.7%, respectively, compared with the pristine carbon fibers reinforced composite. Further, the sample CFRP-3 exhibited higher and more stable friction coefficient and improved wear resistance, while the wear rate decreased 52.7%, from 10.8 × 10-6 to 5.1 × 10-6 mm3/N m. The present work shows that grafting methyl acrylic via Diels-Alder reaction could be a highly efficient and facile method to functionalize carbon fibers for advanced composites.
Characterizing multiple metal ion binding sites within a ribozyme by cadmium-induced EPR silencing
Kisseleva, Natalia; Kraut, Stefanie; Jäschke, Andres; Schiemann, Olav
2007-01-01
In ribozyme catalysis, metal ions are generally known to make structural and∕or mechanistic contributions. The catalytic activity of a previously described Diels-Alderase ribozyme was found to depend on the concentration of divalent metal ions, and crystallographic data revealed multiple binding sites. Here, we elucidate the interactions of this ribozyme with divalent metal ions in solution using electron paramagnetic resonance (EPR) spectroscopy. Manganese ion titrations revealed five high-affinity Mn2+ binding sites with an upper Kd of 0.6±0.2 μM. In order to characterize each binding site individually, EPR-silent Cd2+ ions were used to saturate the other binding sites. This cadmium-induced EPR silencing showed that the Mn2+ binding sites possess different affinities. In addition, these binding sites could be assigned to three different types, including innersphere, outersphere, and a Mn2+ dimer. Based on simulations, the Mn2+-Mn2+ distance within the dimer was found to be ∼6 Å, which is in good agreement with crystallographic data. The EPR-spectroscopic characterization reveals no structural changes upon addition of a Diels-Alder product, supporting the concept of a preorganized catalytic pocket in the Diels-Alder ribozyme and the structural role of these ions. PMID:19404418
Computational design of a Diels-Alderase from a thermophilic esterase: the importance of dynamics
NASA Astrophysics Data System (ADS)
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 effect of pressure on microwave-enhanced Diels-Alder reactions. A case study.
Kaval, Nadya; Dehaen, Wim; Kappe, C Oliver; Van der Eycken, Erik
2004-01-21
It is demonstrated that microwave-assisted Diels-Alder reactions of substituted 2(1H)-pyrazinones with ethylene are significantly more effective utilizing pre-pressurized (up to 10 bar) reaction vessels.
Role of Biotic and Abiotic Processes on Soil CO2 Dynamics in the McMurdo Dry Valleys, Antarctica
NASA Astrophysics Data System (ADS)
Risk, D. A.; Macintyre, C. M.; Lee, C.; Cary, C.; Shanhun, F.; Almond, P. C.
2016-12-01
In the harsh conditions of the Antarctic Dry Valleys, microbial activity has been recorded via measurements of soil carbon dioxide (CO2) concentration and surface efflux. However, high temporal resolution studies in the Dry Valleys have also shown that abiotic solubility-driven processes can strongly influence (and perhaps even dominate) the CO2 dynamics in these low flux environments and suggests that biological activity may be lower than previously thought. In this study, we aim to improve our understanding of CO2 dynamics (biotic and abiotic) in Antarctic Dry Valley soils using long-term automated measurements of soil CO2 surface flux and soil profile concentration at several sites, often at sub-diel frequency. We hypothesize that soil CO2 variations are driven primarily by environmental factors affecting CO2 solubility in soil solution, mainly temperature, and that these processes may even overprint biologic production in representative Dry Valley soils. Monitoring of all sites revealed only one likely biotic CO2 production event, lasting three weeks during the Austral summer and reaching fluxes of 0.4 µmol/m2/s. Under more typical low flux conditions (<0.10 µmol/m2/s) we observed a cyclical daily sink/source pattern consistent with CO2 solubility cycling that would not generally have been evident with normal synoptic afternoon sampling campaigns. Subsurface CO2 monitoring and a lab-controlled Antarctic soil simulation experiment confirmed that abiotic processes are capable of dominating soil CO2 variability. Diel temperature cycles crossing the freezing boundary revealed a dual abiotic cycle of solubility cycling and gas exclusion from ice formation observed only by high temporal frequency measurements (30 min). This work demonstrates a need for a numerical model to partition the dynamic abiotic processes underlying any biotic CO2 production in order to understand potential climate-change induced increases in microbial productivity in terrestrial Antarctica.
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.
Kissane, Marie; Lynch, Denis; Chopra, Jay; Lawrence, Simon E; Maguire, Anita R
2010-12-21
The Diels-Alder cycloadditions of cyclopentadiene and 2,3-dimethyl-1,3-butadiene to a range of 2-thio-3-chloroacrylamides under thermal, catalytic and microwave conditions is described. The influence of reaction conditions on the outcome of the cycloadditions, in particular the stereoselectivity and reaction efficiency, is discussed. While the cycloadditions have been attempted at the sulfide, sulfoxide and sulfone levels of oxidation, use of the sulfoxide derivatives is clearly beneficial for stereoselective construction of Diels-Alder cycloadducts.
NASA Astrophysics Data System (ADS)
VanReken, Timothy M.; Dhammapala, Ranil S.; Jobson, B. Thomas; Bottenus, Courtney L.; VanderSchelden, Graham S.; Kaspari, Susan D.; Gao, Zhongming; Zhu, Qiurui; Lamb, Brian K.; Liu, Heping; Johnston, Jeff
2017-04-01
The Yakima Air Wintertime Nitrate Study (YAWNS) was conducted in January 2013 to investigate the drivers of elevated levels of fine particulate matter (PM2.5) frequently present in the region during winter stagnation periods. An extended stagnation period occurred during the study. For the first four days of the event, skies were clear and the strong diel variation in air pollution patterns were consistent with the expected effects of strong low-level nighttime temperature inversions with moderate mixing during daylight hours. Later in the event a low-level cloud layer formed that persisted over the Yakima Valley for the next seven days while regional conditions remained stagnant. Coincident with the onset of cloud, the levels of all measured primary pollutants, including CO2, CO, NOx, particle number concentration, and black carbon, dropped dramatically and remained low with negligible diel variation for as long as the cloud layer was present. The observed patterns for these air pollutants are consistent with decreased stability and enhanced mixing associated with the cloud-topped boundary layer. Interestingly, levels of secondary pollutants, most notably particulate ammonium nitrate, did not exhibit the same decline. This difference may be due to shifts in the chemical production of secondary pollutants during cloudy conditions, or may merely reflect a further influence of mixing. The results imply that the best strategies for managing wintertime air quality during episodes of persistent cloud are likely different from those needed during clear-sky stagnation events.
Johnson, J. H.; Ross, R.M.; Dropkin, D.S.; Redell, L.A.
2011-01-01
Although considerable information exists on habitat use by stream salmonids, only a small portion has quantitatively examined diurnal and nocturnal habitat variation. We examined diel variation in habitat use by age-0 and age-1+ brook trout (Salvelinus fontinalis) during summer and autumn in a headwater stream in northern Pennsylvania. Habitat variables measured included cover, depth, substrate, and velocity. The most pronounced diel variation occurred in the use of cover during both seasons. Both age-0 brook trout and age-1+ trout were associated with less cover at night. Age-0 brook trout occupied swifter water during the day than at night during both seasons, but the difference was not significant. Increased cover, depth, and substrate size governed the habitat of age-1+ brook trout. Our findings support the need for a better understanding of diel differences in habitat use of stream salmonids when considering habitat enhancement and protection.
Coe, Allison; Roggensack, Sara E.
2018-01-01
ABSTRACT Microbes evolve within complex ecological communities where biotic interactions impact both individual cells and the environment as a whole. Here we examine how cellular regulation in the marine cyanobacterium Prochlorococcus is influenced by a heterotrophic bacterium, Alteromonas macleodii, under different light conditions. We monitored the transcriptome of Prochlorococcus, grown either alone or in coculture, across a diel light:dark cycle and under the stress of extended darkness—a condition that cells would experience when mixed below the ocean’s euphotic zone. More Prochlorococcus transcripts exhibited 24-h periodic oscillations in coculture than in pure culture, both over the normal diel cycle and after the shift to extended darkness. This demonstrates that biotic interactions, and not just light, can affect timing mechanisms in Prochlorococcus, which lacks a self-sustaining circadian oscillator. The transcriptomes of replicate pure cultures of Prochlorococcus lost their synchrony within 5 h of extended darkness and reflected changes in stress responses and metabolic functions consistent with growth cessation. In contrast, when grown with Alteromonas, replicate Prochlorococcus transcriptomes tracked each other for at least 13 h in the dark and showed signs of continued biosynthetic and metabolic activity. The transcriptome patterns suggest that the heterotroph may be providing energy or essential biosynthetic substrates to Prochlorococcus in the form of organic compounds, sustaining this autotroph when it is deprived of solar energy. Our findings reveal conditions where mixotrophic metabolism may benefit marine cyanobacteria and highlight new impacts of community interactions on basic Prochlorococcus cellular processes. IMPORTANCE Prochlorococcus is the most abundant photosynthetic organism on the planet. These cells play a central role in the physiology of surrounding heterotrophs by supplying them with fixed organic carbon. It is becoming increasingly clear, however, that interactions with heterotrophs can affect autotrophs as well. Here we show that such interactions have a marked impact on the response of Prochlorococcus to the stress of extended periods of darkness, as reflected in transcriptional dynamics. These data suggest that diel transcriptional rhythms within Prochlorococcus, which are generally considered to be strictly under the control of light quantity, quality, and timing, can also be influenced by biotic interactions. Together, these findings provide new insights into the importance of microbial interactions on Prochlorococcus physiology and reveal conditions where heterotroph-derived compounds may support autotrophs—contrary to the canonical autotroph-to-heterotroph trophic paradigm. PMID:29854954
Lehmann, M M; Wegener, F; Werner, R A; Werner, C
2016-09-01
Leaf respiration in the dark and its C isotopic composition (δ(13) CR ) contain information about internal metabolic processes and respiratory substrates. δ(13) CR is known to be less negative compared to potential respiratory substrates, in particular shortly after darkening during light enhanced dark respiration (LEDR). This phenomenon might be driven by respiration of accumulated (13) C-enriched organic acids, however, studies simultaneously measuring δ(13) CR during LEDR and potential respiratory substrates are rare. We determined δ(13) CR and respiration rates (R) during LEDR, as well as δ(13) C and concentrations of potential respiratory substrates using compound-specific isotope analyses. The measurements were conducted throughout the diel cycle in several plant species under different environmental conditions. δ(13) CR and R patterns during LEDR were strongly species-specific and showed an initial peak, which was followed by a progressive decrease in both values. The species-specific differences in δ(13) CR and R during LEDR may be partially explained by the isotopic composition of organic acids (e.g., oxalate, isocitrate, quinate, shikimate, malate), which were (13) C-enriched compared to other respiratory substrates (e.g., sugars and amino acids). However, the diel variations in both δ(13) C and concentrations of the organic acids were generally low. Thus, additional factors such as the heterogeneous isotope distribution in organic acids and the relative contribution of the organic acids to respiration are required to explain the strong (13) C enrichment in leaf dark-respired CO2 . © 2016 German Botanical Society and The Royal Botanical Society of the Netherlands.
Quiroga, Jairo; Villarreal, Yazmín; Gálvez, Jaime; Ortíz, Alejandro; Insuasty, Braulio; Abonia, Rodrigo; Raimondi, Marcela; Zacchino, Susana
2017-02-01
A series of pyrazolo[3,4-b]pyridines were prepared by a microwave-assisted aza-Diels-Alder reaction between pyrazolylformimidamides 1 and β-nitrostyrenes 2 in toluene as the solvent. This procedure provides a simple one-step and environmentally friendly methodology with good yields for the synthesis of these compounds. All compounds were tested for antifungal activity against two clinically important fungi Candida albicans and Cryptococcus neoformans. Within the compounds of the series bearing a -CH 3 group on the carbon C-3 of the azole ring (3a-e), the compound without a substituent on the p'-phenyl ring (3a), showed the best activity against both fungi, followed by the p'-Br-phenyl (3c). Within the compounds of the series bearing a tert-butyl group in the carbon C-3 of the azole ring (3f-j), the non-substituted p'-compound (3f) was the most active one, followed by (3h) (p'-Br substituted) that showed the best activity against both fungi. The remaining compounds of this sub-series (3g, i, j) showed similar moderate activities. The antifungal activity of the compounds of the series was found to be correlated with a higher log P and a lower dipole moment in the more active compounds.
Comparison of Techniques for Sampling Adult Necrophilous Insects From Pig Carcasses.
Cruise, Angela; Hatano, Eduardo; Watson, David W; Schal, Coby
2018-02-06
Studies of the pre-colonization interval and mechanisms driving necrophilous insect ecological succession depend on effective sampling of adult insects and knowledge of their diel and successional activity patterns. The number of insects trapped, their diversity, and diel periodicity were compared with four sampling methods on neonate pigs. Sampling method, time of day and decomposition age of the pigs significantly affected the number of insects sampled from pigs. We also found significant interactions of sampling method and decomposition day, time of sampling and decomposition day. No single method was superior to the other methods during all three decomposition days. Sampling times after noon yielded the largest samples during the first 2 d of decomposition. On day 3 of decomposition however, all sampling times were equally effective. Therefore, to maximize insect collections from neonate pigs, the method used to sample must vary by decomposition day. The suction trap collected the most species-rich samples, but sticky trap samples were the most diverse, when both species richness and evenness were factored into a Shannon diversity index. Repeated sampling during the noon to 18:00 hours period was most effective to obtain the maximum diversity of trapped insects. The integration of multiple sampling techniques would most effectively sample the necrophilous insect community. However, because all four tested methods were deficient at sampling beetle species, future work should focus on optimizing the most promising methods, alone or in combinations, and incorporate hand-collections of beetles. © The Author(s) 2018. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.
NASA Astrophysics Data System (ADS)
Bebout, B.; Bebout, L. E.; Detweiler, A. M.; Everroad, R. C.; Lee, J.; Pett-Ridge, J.; Weber, P. K.
2014-12-01
Microbial mats are famously amongst the most diverse microbial ecosystems on Earth, inhabiting some of the most inclement environments known, including hypersaline, dry, hot, cold, nutrient poor, and high UV environments. The high microbial diversity of microbial mats makes studies of microbial ecology notably difficult. To address this challenge, we have been using a combination of metagenomics, metatranscriptomics, iTags and culture-based simplified microbial mats to study biogeochemical cycling (H2 production, N2 fixation, and fermentation) in microbial mats collected from Elkhorn Slough, Monterey Bay, California. Metatranscriptomes of microbial mats incubated over a diel cycle have revealed that a number of gene systems activate only during the day in Cyanobacteria, while the remaining appear to be constitutive. The dominant cyanobacterium in the mat (Microcoleus chthonoplastes) expresses several pathways for nitrogen scavenging undocumented in cultured strains, as well as the expression of two starch storage and utilization cycles. Community composition shifts in response to long term manipulations of mats were assessed using iTags. Changes in community diversity were observed as hydrogen fluxes increased in response to a lowering of sulfate concentrations. To produce simplified microbial mats, we have isolated members of 13 of the 15 top taxa from our iTag libraries into culture. Simplified microbial mats and simple co-cultures and consortia constructed from these isolates reproduce many of the natural patterns of biogeochemical cycling in the parent natural microbial mats, but against a background of far lower overall diversity, simplifying studies of changes in gene expression (over the short term), interactions between community members, and community composition changes (over the longer term), in response to environmental forcing.
Plumb, John M.; Adams, Noah S.; Perry, Russell W.; Holbrook, Christopher; Romine, Jason G.; Blake, Aaron R.; Burau, Jon R.
2016-01-01
In the Sacramento-San Joaquin River Delta, California, tidal forces that reverse river flows increase the proportion of water and juvenile late fall-run Chinook salmon diverted into a network of channels that were constructed to support agriculture and human consumption. This area is known as the interior delta, and it has been associated with poor fish survival. Under the rationale that the fish will be diverted in proportion to the amount of water that is diverted, the Delta Cross Channel (DCC) has been prescriptively closed during the winter out-migration to reduce fish entrainment and mortality into the interior delta. The fish are thought to migrate mostly at night, and so daytime operation of the DCC may allow for water diversion that minimizes fish entrainment and mortality. To assess this, the DCC gate was experimentally opened and closed while we released 2983 of the fish with acoustic transmitters upstream of the DCC to monitor their arrival and entrainment into the DCC. We used logistic regression to model night-time arrival and entrainment probabilities with covariates that included the proportion of each diel period with upstream flow, flow, rate of change in flow and water temperature. The proportion of time with upstream flow was the most important driver of night-time arrival probability, yet river flow had the largest effect on fish entrainment into the DCC. Modelling results suggest opening the DCC during daytime while keeping the DCC closed during night-time may allow for water diversion that minimizes fish entrainment into the interior delta.
Diel Vertical Migration Thresholds of Karenia brevis (Dinophyceae).
Light and nutrient availability change throughout dinoflagellate diel vertical migration (DVM) and/or with subpopulation location in the water column along the west Florida shelf. Typically, the vertical depth of the shelf is greater than the distance a subpopulation can vertical...
The Preparation and Properties of Thermo-reversibly Cross-linked Rubber Via Diels-Alder Chemistry.
Polgar, Lorenzo Massimo; van Duin, Martin; Picchioni, Francesco
2016-08-25
A method for using Diels Alder thermo-reversible chemistry as cross-linking tool for rubber products is demonstrated. In this work, a commercial ethylene-propylene rubber, grafted with maleic anhydride, is thermo-reversibly cross-linked in two steps. The pending anhydride moieties are first modified with furfurylamine to graft furan groups to the rubber backbone. These pendant furan groups are then cross-linked with a bis-maleimide via a Diels-Alder coupling reaction. Both reactions can be performed under a broad range of experimental conditions and can easily be applied on a large scale. The material properties of the resulting Diels-Alder cross-linked rubbers are similar to a peroxide-cured ethylene/propylene/diene rubber (EPDM) reference. The cross-links break at elevated temperatures (> 150 °C) via the retro-Diels-Alder reaction and can be reformed by thermal annealing at lower temperatures (50-70 °C). Reversibility of the system was proven with infrared spectroscopy, solubility tests and mechanical properties. Recyclability of the material was also shown in a practical way, i.e., by cutting a cross-linked sample into small parts and compression molding them into new samples displaying comparable mechanical properties, which is not possible for conventionally cross-linked rubbers.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Espeleta, Javier F.; Cardon, Zoe G.; Mayer, K. Ulrich
Hydro-biogeochemical processes in the rhizosphere regulate nutrient and water availability, and thus ecosystem productivity. We hypothesized that two such processes often neglected in rhizosphere models — diel plant water use and competitive cation exchange — could interact to enhance availability of K + and NH 4 +, both high-demand nutrients. A rhizosphere model with competitive cation exchange was used to investigate how diel plant water use (i.e., daytime transpiration coupled with no nighttime water use, with nighttime root water release, and with nighttime transpiration) affects competitive ion interactions and availability of K + and NH 4 +. Competitive cation exchangemore » enabled lowdemand cations that accumulate against roots (Ca 2+, Mg 2+, Na +) to desorb NH 4 + and K + from soil, generating non-monotonic dissolved concentration profiles (i.e. ‘hotspots’ 0.1–1 cm from the root). Cation accumulation and competitive desorption increased with net root water uptake. Daytime transpiration rate controlled diel variation in NH 4 + and K + aqueous mass, nighttime water use controlled spatial locations of ‘hotspots’, and day-to-night differences in water use controlled diel differences in ‘hotspot’ concentrations. Finally, diel plant water use and competitive cation exchange enhanced NH 4 + and K + availability and influenced rhizosphere concentration dynamics. Demonstrated responses have implications for understanding rhizosphere nutrient cycling and plant nutrient uptake.« less
SPATIAL AND DIEL AVAILABILITY OF FLYING INSECTS AS POTENTIAL DUCKLING FOOD IN PRAIRIE WETLANDS.
The study examined spatial and diel availibility of flying insects that are a critical food resource to young duckings. Insects were sampled in three native prairie wetlands on the Woodworth Study Area of south-central North Dakota.
Light and lunar cycle as cues to diel migration of a sound-scattering layer
NASA Astrophysics Data System (ADS)
Benoit-Bird, Kelly J.; Au, Whitlow W. L.
2001-05-01
The Hawaiian mesopelagic boundary community is an island-associated midwater scattering layer comprised of small fishes, shrimps, and squids that undergoes diel vertical as well as horizontal migrations. It has been hypothesized that light levels are an important cue or trigger for vertical migration and presumably, horizontal migration. The migration pattern of the scattering layer was measured over complete lunar cycles while the incident light levels were recorded. Due to differences in the rise and set times of the moon and cloud cover, light and lunar cycle were not completely coupled, allowing separation of the light effects of moon phase and other cues associated with lunar cycle. Four calibrated echosounder moorings were deployed with approximately even spacing, perpendicular to the leeward coast of Oahu. Moorings were deployed for one complete lunar cycle at each of three locations, recording 10 echoes every 15 min. Light sensors measured the nocturnal light intensity at 30-s intervals. Statistical analysis revealed significant effects of both light and other lunar cycle cues. Overall, the effect size was very low considering the light transmission characteristics of the subtropical Pacific, making measurement from stationary acoustic platforms critical.
Liu, Yang; Wu, Boran; Hao, Yongxia; Zhu, Wei; Li, Zhonggen; Chai, Xiaoli
2017-01-01
Mercury emission fluxes (MEFs) under different surface coverage conditions in a landfill were investigated in this study. The results show similar diel patterns of Hg emission flux under different coverage conditions, with peak fluxes occurring at midday and decreasing during night. We examined the effects of environmental factors on MEFs, such as the physiological characteristics of vegetation and meteorological conditions. The results suggest that growth of vegetation in the daytime facilitates the release of Hg in the anaerobic unit, while in the semi-aerobic unit, where vegetation had been removed, the higher mercury content of the cover soil prompted the photo-reduction pathway to become the main path of mercury release and increased MEFs. MEFs are positively correlated with solar radiation and air temperature, but negatively correlated with relative humidity. The correlation coefficients for MEFs with different environmental parameters indicate that in the anaerobic unit, solar radiation was the main influence on MEFs in September, while air temperature became the main determining factor in December. These observations suggest that the effects of meteorological conditions on the mercury release mechanism varies depending on the vegetation and soil pathways. Copyright © 2016. Published by Elsevier Ltd.
Diel drift of Chironomidae larvae in a pristine Idaho mountain stream
Tilley, L.J.
1989-01-01
Simultaneous hourly net collections in a meadow and canyon reach of a mountain stream determined diel and spatial abundances of drifting Chironomidae larvae. Sixty-one taxa were identified to the lowest practical level, 52 in the meadow and 41 in the canyon. Orthocladiinae was the most abundant subfamily with 32 taxa and a 24 h mean density of 294 individuals 100 m-3 (meadow) and 26 taxa and a mean of 648 individuals 100 m-3 (canyon). Chironominae was the second most abundant subfamily. Nonchironomid invertebrates at both sites and total Chironomidae larvae (meadow) were predominantly night-drifting. Parakiefferiella and Psectrocladius were day-drifting (meadow) whereas 8 other chironomid taxa (meadow) and 2 taxa (canyon) were night-drifting. All others were aperiodic or too rare to test periodicity, Stempellinella cf brevis Edwards exhibited catastrophic drift in the canyon only. The different drift patterns between sites is attributed to greater loss of streambed habitat in the canyon compared to the meadow as streamflow decreased. Consequent crowding of chironomid larvae in the canyon caused catastrophic drift or interfered with drift periodicty. This study adds to knowledge of Chironomidae drift and shows influences on drift of hydrologic and geomorphic conditions. ?? 1989 Kluwer Academic Publishers.
Mohr, Claudia; Lopez-Hilfiker, Felipe D.; Lutz, Anna; Hallquist, Mattias; Lee, Lance; Romer, Paul; Cohen, Ronald C.; Iyer, Siddharth; Kurtén, Theo; Hu, Weiwei; Day, Douglas A.; Campuzano-Jost, Pedro; Jimenez, Jose L.; Xu, Lu; Ng, Nga Lee; Guo, Hongyu; Weber, Rodney J.; Wild, Robert J.; Brown, Steven S.; Koss, Abigail; de Gouw, Joost; Olson, Kevin; Goldstein, Allen H.; Seco, Roger; Kim, Saewung; McAvey, Kevin; Shepson, Paul B.; Starn, Tim; Baumann, Karsten; Edgerton, Eric S.; Liu, Jiumeng; Shilling, John E.; Miller, David O.; Brune, William; Schobesberger, Siegfried; D'Ambro, Emma L.; Thornton, Joel A.
2016-01-01
Speciated particle-phase organic nitrates (pONs) were quantified using online chemical ionization MS during June and July of 2013 in rural Alabama as part of the Southern Oxidant and Aerosol Study. A large fraction of pONs is highly functionalized, possessing between six and eight oxygen atoms within each carbon number group, and is not the common first generation alkyl nitrates previously reported. Using calibrations for isoprene hydroxynitrates and the measured molecular compositions, we estimate that pONs account for 3% and 8% of total submicrometer organic aerosol mass, on average, during the day and night, respectively. Each of the isoprene- and monoterpenes-derived groups exhibited a strong diel trend consistent with the emission patterns of likely biogenic hydrocarbon precursors. An observationally constrained diel box model can replicate the observed pON assuming that pONs (i) are produced in the gas phase and rapidly establish gas–particle equilibrium and (ii) have a short particle-phase lifetime (∼2–4 h). Such dynamic behavior has significant implications for the production and phase partitioning of pONs, organic aerosol mass, and reactive nitrogen speciation in a forested environment. PMID:26811465
Empirical evaluation of predator-driven diel vertical migration in Lake Superior
Stockwell, J.D.; Hrabik, T.R.; Jensen, O.P.; Yule, D.L.; Balge, M.
2010-01-01
Recent studies on Lake Superior suggest that diel vertical migration (DVM) of prey (generalized Coregonus spp.) may be influenced by the density of predatory siscowet (Salvelinus namaycush). We empirically evaluated this hypothesis using data from acoustic, midwater trawl, and bottom trawl sampling at eight Lake Superior sites during three seasons in 2005 and a subset of sites in 2006. We expected the larger-bodied cisco (Coregonus artedi) to exhibit a shallower DVM compared with the smaller-bodied kiyi (Coregonus kiyi). Although DVM of kiyi and cisco were consistent with expectations of DVM as a size-dependent, predator-mediated process, we found no relationship between siscowet density and the magnitude of DVM of either coregonid. Cisco appear to have a size refuge from siscowet predation. Kiyi and siscowet co-occur in demersal habitat > 150 m during the day, where visual predation is unlikely, suggesting predator avoidance is not a factor in the daytime distribution of kiyi. Seasonal patterns of kiyi DVM were consistent with reported DVM of their primary prey Mysis relicta. Our results suggest that consideration of nonvisual foraging, rather than lightbased foraging theory (i.e., the antipredation window), is necessary to understand the processes driving DVM in deepwater systems.
Survival, mortality, and predators of red tree voles (Arborimus longicaudus)
James K. Swingle; Eric D. Forsman; Robert G. Anthony
2010-01-01
Although estimations of vital rates are important to understand population dynamics of small mammals, there is little information on survival rates and causes of mortality for many species. In 2002-2003, we estimated monthly and annual survival of 50 radiocollared red tree voles (Arborimus longicaudus) during a study of movements and diel activity...
An MM and QM Study of Biomimetic Catalysis of Diels-Alder Reactions Using Cyclodextrins
Chen, Wei; Sun, Lipeng; Tang, Zhiye; Ali, Zulfikhar A.; Wong, Bryan M.; Chang, Chia-en A.
2018-01-01
We performed a computational investigation of the mechanism by which cyclodextrins (CDs) catalyze Diels-Alder reactions between 9-anthracenemethanol and N-cyclohexylmaleimide. Hydrogen bonds (Hbonds) between N-cyclohexylmaleimide and the hydroxyl groups of cyclodextrins were suggested to play an important role in this catalytic process. However, our free energy calculations and molecular dynamics simulations showed that these Hbonds are not stable, and quantum mechanical calculations suggested that the reaction is not promoted by these Hbonds. The binding of 9-anthracenemethanol and N-cyclohexylmaleimide to cyclodextrins was the key to the catalytic process. Cyclodextrins act as a container to hold the two reactants in the cavity, pre-organize them for the reactions, and thus reduce the entropy penalty to the activation free energy. Dimethyl-β-CD was a better catalyst for this specific reaction than β-CD because of its stronger van der Waals interaction with the pre-organized reactants and its better performance in reducing the activation energy. This computational work sheds light on the mechanism of the catalytic reaction by cyclodextrins and introduces new perspectives of supramolecular catalysis. PMID:29938117
A recyclable fluorous organocatalyst for Diels-Alder reactions
Chu, Qianli; Zhang, Wei; Curran, Dennis P.
2007-01-01
Chiral fluorous imidazolidinone catalyst 2 provides consistently high enantioselectivities in Diels-Alder reactions of dienes and α, β-unsaturated aldehydes. The catalyst can be readily separated from the reaction products by fluorous solid-phase extraction, and recovered in excellent purity for direct reuse. PMID:17710220
Temporal and Spatial Dynamics of Diel-Cycling Hypoxia in Four Northern Gulf of Mexico Estuaries
Eutrophication of coastal ecosystems has accelerated in recent decades due to population growth and associated nutrient pollution, resulting in increased incidence of hypoxia. Shallow and highly productive estuaries and embayments are particularly susceptible to diel-cycling hypo...
SAM-dependent enzyme-catalysed pericyclic reactions in natural product biosynthesis
NASA Astrophysics Data System (ADS)
Ohashi, Masao; Liu, Fang; Hai, Yang; Chen, Mengbin; Tang, Man-Cheng; Yang, Zhongyue; Sato, Michio; Watanabe, Kenji; Houk, K. N.; Tang, Yi
2017-09-01
Pericyclic reactions—which proceed in a concerted fashion through a cyclic transition state—are among the most powerful synthetic transformations used to make multiple regioselective and stereoselective carbon-carbon bonds. They have been widely applied to the synthesis of biologically active complex natural products containing contiguous stereogenic carbon centres. Despite the prominence of pericyclic reactions in total synthesis, only three naturally existing enzymatic examples (the intramolecular Diels-Alder reaction, and the Cope and the Claisen rearrangements) have been characterized. Here we report a versatile S-adenosyl-L-methionine (SAM)-dependent enzyme, LepI, that can catalyse stereoselective dehydration followed by three pericyclic transformations: intramolecular Diels-Alder and hetero-Diels-Alder reactions via a single ambimodal transition state, and a retro-Claisen rearrangement. Together, these transformations lead to the formation of the dihydropyran core of the fungal natural product, leporin. Combined in vitro enzymatic characterization and computational studies provide insight into how LepI regulates these bifurcating biosynthetic reaction pathways by using SAM as the cofactor. These pathways converge to the desired biosynthetic end product via the (SAM-dependent) retro-Claisen rearrangement catalysed by LepI. We expect that more pericyclic biosynthetic enzymatic transformations remain to be discovered in naturally occurring enzyme ‘toolboxes’. The new role of the versatile cofactor SAM is likely to be found in other examples of enzyme catalysis.
Xu, Hong De; Cho, Soon-Chang; Bang, Mi-Ae; Bae, Chun-Sik; Choi, Yeonshik; Li, Yong-Chun; Lim, Seung-Kil; Shim, Jaegal; Park, Dae-Hun
2015-01-01
The World Health Organization (WHO) has reported that cancer is one of the most prevalent diseases and a leading cause of death worldwide. Many anticancer drug development studies have been pursued over the last few decades and several viable drugs have been discovered, such as paclitaxel, topotecan and irinotecan. Previously, our research group uncovered the cytocidal and cytostatic effects of the plant Stephania delavayi Diels. In this study, we determined the active chemical to be 6,7-di-O-acetylsinococuline (FK-3000). The FK-3000 half maximal inhibitory concentration (IC50) in MDA-MB-231 breast carcinoma cells at 48 h was 0.52 µg/ml and it induced apoptosis in a dose- and time-dependent manner. FK-3000 suppressed NF-κB nuclear translocation, decreased NF-κB phosphorylation, and decreased COX-2 protein expression. MDA-MB-231 xenografted mice were treated with FK-3000, Taxol, or their combination for 21 days. The tumor size was smallest in the co-treatment group, indicating that FK-3000 may have a synergistic effect with Taxol. FK-3000 treatment showed no adverse effects on blood cell counts, serum protein levels, or pathology. These studies demonstrate that FK-3000, isolated from S. delavayi Diels., is a promising, pathway-specific anticancer agent that exhibits low toxicity.
NASA Astrophysics Data System (ADS)
Maycas, Encarna Ribera; Bourdillon, André; Macquart-Moulin, Claude; Passelaigue, Françoise; Patriti, Gilbert
1999-10-01
The bathymetric distribution, abundance and diel vertical migrations (DVM) of zooplankton were investigated along the axis of the Cap-Ferret Canyon (Bay of Biscay, French Atlantic coast) by a consecutive series of synchronous net hauls that sampled the whole water column (0-2000 m in depth) during a diel cycle. The distribution of appendicularians (maximum 189 individuals m -3), cladocerans (maximum 287 individuals m -3), copepods (copepods<4 mm, maximum 773 individuals m -3, copepods>4 mm, maximum 13 individuals m -3), ostracods (maximum 8 individuals m -3), siphonophores (maximum >2 individuals m -3) and peracarids (maximum >600 individuals 1000 m -3) were analysed and represented by isoline diagrams. The biomass of total zooplankton (maximum 18419 μg C m -3, 3780 μg N m -3) and large copepods (>4 mm maximum 2256 μg C m -3, 425 μg N m -3) also were determined. Vertical migration was absent or affected only the epipelagic zone for appendicularians, cladocerans, small copepods and siphonophores. Average amplitude of vertical migration was about 400-500 m for ostracods, some hyperiids and mysids, and large copepods, which were often present in the epipelagic, mesopelagic, and bathypelagic zones. Large copepods can constitute more than 80% of the biomass corresponding to total zooplankton. They may play an important role in the active vertical transfer of carbon and nitrogen.
NASA Astrophysics Data System (ADS)
Banella, Maria Barbara; Gioia, Claudio; Vannini, Micaela; Colonna, Martino; Celli, Annamaria; Gandini, Alessandro
2016-05-01
The Diels-Alder reaction between furan and maleimide moieties is a well-known and widely used strategy to build bio-based macromolecular structures with peculiar properties. The furan-maleimide adducts are thermally reversible because they can be broken above about 120°C and recombined at lower temperatures. At the moment only the monomers exhibiting the furan or the maleimide moieties on their extremity are used in order to get linear or cross-linked polymeric structures. The innovative idea described here consists in using a monomer bearing two carboxylic acidic groups on its extremities and a furan-maleimide Diels-Alder adduct within its structure. This monomer can give rise to classical polycondensation reactions leading to polymers. These polymers (which are polyesters in the present case) can be broken at high temperatures in correspondence of the furane-maleimide Diels-Alder adduct leading to segments exhibiting furan or maleimide moieties at their extremities, which at lower temperature recombine leading to random or block copolymers.
NASA Astrophysics Data System (ADS)
Nicholson, David P.; Wilson, Samuel T.; Doney, Scott C.; Karl, David M.
2015-05-01
Using autonomous underwater gliders, we quantified diurnal periodicity in dissolved oxygen, chlorophyll, and temperature in the subtropical North Pacific near the Hawaii Ocean Time-series (HOT) Station ALOHA during summer 2012. Oxygen optodes provided sufficient stability and precision to quantify diel cycles of average amplitude of 0.6 µmol kg-1. A theoretical diel curve was fit to daily observations to infer an average mixed layer gross primary productivity (GPP) of 1.8 mmol O2 m-3 d-1. Cumulative net community production (NCP) over 110 days was 500 mmol O2 m-2 for the mixed layer, which averaged 57 m in depth. Both GPP and NCP estimates indicated a significant period of below-average productivity at Station ALOHA in 2012, an observation confirmed by 14C productivity incubations and O2/Ar ratios. Given our success in an oligotrophic gyre where biological signals are small, our diel GPP approach holds promise for remote characterization of productivity across the spectrum of marine environments.
Matthews, Leanna P.; McCordic, Jessica A.; Parks, Susan E.
2014-01-01
Remote acoustic monitoring is a non-invasive tool that can be used to study the distribution, behavior, and habitat use of sound-producing species. The North Atlantic right whale (Eubalaena glacialis) is an endangered baleen whale species that produces a variety of stereotyped acoustic signals. One of these signals, the “gunshot” sound, has only been recorded from adult male North Atlantic right whales and is thought to function for reproduction, either as reproductive advertisement for females or as an agonistic signal toward other males. This study uses remote acoustic monitoring to analyze the presence of gunshots over a two-year period at two sites on the Scotian Shelf to determine if there is evidence that North Atlantic right whales may use these locations for breeding activities. Seasonal analyses at both locations indicate that gunshot sound production is highly seasonal, with an increase in the autumn. One site, Roseway West, had significantly more gunshot sounds overall and exhibited a clear diel trend in production of these signals at night. The other site, Emerald South, also showed a seasonal increase in gunshot production during the autumn, but did not show any significant diel trend. This difference in gunshot signal production at the two sites indicates variation either in the number or the behavior of whales at each location. The timing of the observed seasonal increase in gunshot sound production is consistent with the current understanding of the right whale breeding season, and our results demonstrate that detection of gunshots with remote acoustic monitoring can be a reliable way to track shifts in distribution and changes in acoustic behavior including possible mating activities. PMID:24646524
Matthews, Leanna P; McCordic, Jessica A; Parks, Susan E
2014-01-01
Remote acoustic monitoring is a non-invasive tool that can be used to study the distribution, behavior, and habitat use of sound-producing species. The North Atlantic right whale (Eubalaena glacialis) is an endangered baleen whale species that produces a variety of stereotyped acoustic signals. One of these signals, the "gunshot" sound, has only been recorded from adult male North Atlantic right whales and is thought to function for reproduction, either as reproductive advertisement for females or as an agonistic signal toward other males. This study uses remote acoustic monitoring to analyze the presence of gunshots over a two-year period at two sites on the Scotian Shelf to determine if there is evidence that North Atlantic right whales may use these locations for breeding activities. Seasonal analyses at both locations indicate that gunshot sound production is highly seasonal, with an increase in the autumn. One site, Roseway West, had significantly more gunshot sounds overall and exhibited a clear diel trend in production of these signals at night. The other site, Emerald South, also showed a seasonal increase in gunshot production during the autumn, but did not show any significant diel trend. This difference in gunshot signal production at the two sites indicates variation either in the number or the behavior of whales at each location. The timing of the observed seasonal increase in gunshot sound production is consistent with the current understanding of the right whale breeding season, and our results demonstrate that detection of gunshots with remote acoustic monitoring can be a reliable way to track shifts in distribution and changes in acoustic behavior including possible mating activities.
A high-resolution time-depth view of dimethylsulphide cycling in the surface sea
Royer, S.-J.; Galí, M.; Mahajan, A. S.; Ross, O. N.; Pérez, G. L.; Saltzman, E. S.; Simó, R.
2016-01-01
Emission of the trace gas dimethylsulphide (DMS) from the ocean influences the chemical and optical properties of the atmosphere, and the olfactory landscape for foraging marine birds, turtles and mammals. DMS concentration has been seen to vary across seasons and latitudes with plankton taxonomy and activity, and following the seascape of ocean’s physics. However, whether and how does it vary at the time scales of meteorology and day-night cycles is largely unknown. Here we used high-resolution measurements over time and depth within coherent water patches in the open sea to show that DMS concentration responded rapidly but resiliently to mesoscale meteorological perturbation. Further, it varied over diel cycles in conjunction with rhythmic photobiological indicators in phytoplankton. Combining data and modelling, we show that sunlight switches and tunes the balance between net biological production and abiotic losses. This is an outstanding example of how biological diel rhythms affect biogeochemical processes. PMID:27578300
Impact of scaffold rigidity on the design and evolution of an artificial Diels-Alderase
Preiswerk, Nathalie; Beck, Tobias; Schulz, Jessica D.; Milovník, Peter; Mayer, Clemens; Siegel, Justin B.; Baker, David; Hilvert, Donald
2014-01-01
By combining targeted mutagenesis, computational refinement, and directed evolution, a modestly active, computationally designed Diels-Alderase was converted into the most proficient biocatalyst for [4+2] cycloadditions known. The high stereoselectivity and minimal product inhibition of the evolved enzyme enabled preparative scale synthesis of a single product diastereomer. X-ray crystallography of the enzyme–product complex shows that the molecular changes introduced over the course of optimization, including addition of a lid structure, gradually reshaped the pocket for more effective substrate preorganization and transition state stabilization. The good overall agreement between the experimental structure and the original design model with respect to the orientations of both the bound product and the catalytic side chains contrasts with other computationally designed enzymes. Because design accuracy appears to correlate with scaffold rigidity, improved control over backbone conformation will likely be the key to future efforts to design more efficient enzymes for diverse chemical reactions. PMID:24847076
From Biomass-Derived Furans to Aromatics with Ethanol over Zeolite.
Teixeira, Ivo F; Lo, Benedict T W; Kostetskyy, Pavlo; Stamatakis, Michail; Ye, Lin; Tang, Chiu C; Mpourmpakis, Giannis; Tsang, Shik Chi Edman
2016-10-10
We report a novel catalytic conversion of biomass-derived furans and alcohols to aromatics over zeolite catalysts. Aromatics are formed via Diels-Alder cycloaddition with ethylene, which is produced in situ from ethanol dehydration. The use of liquid ethanol instead of gaseous ethylene, as the source of dienophile in this one-pot synthesis, makes the aromatics production much simpler and renewable, circumventing the use of ethylene at high pressure. More importantly, both our experiments and theoretical studies demonstrate that the use of ethanol instead of ethylene, results in significantly higher rates and higher selectivity to aromatics, due to lower activation barriers over the solid acid sites. Synchrotron-diffraction experiments and proton-affinity calculations clearly suggest that a preferred protonation of ethanol over the furan is a key step facilitating the Diels-Alder and dehydration reactions in the acid sites of the zeolite. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
A high-resolution time-depth view of dimethylsulphide cycling in the surface sea
NASA Astrophysics Data System (ADS)
Royer, S.-J.; Galí, M.; Mahajan, A. S.; Ross, O. N.; Pérez, G. L.; Saltzman, E. S.; Simó, R.
2016-08-01
Emission of the trace gas dimethylsulphide (DMS) from the ocean influences the chemical and optical properties of the atmosphere, and the olfactory landscape for foraging marine birds, turtles and mammals. DMS concentration has been seen to vary across seasons and latitudes with plankton taxonomy and activity, and following the seascape of ocean’s physics. However, whether and how does it vary at the time scales of meteorology and day-night cycles is largely unknown. Here we used high-resolution measurements over time and depth within coherent water patches in the open sea to show that DMS concentration responded rapidly but resiliently to mesoscale meteorological perturbation. Further, it varied over diel cycles in conjunction with rhythmic photobiological indicators in phytoplankton. Combining data and modelling, we show that sunlight switches and tunes the balance between net biological production and abiotic losses. This is an outstanding example of how biological diel rhythms affect biogeochemical processes.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Burns, S. P.; Blanken, P. D.; Turnipseed, A. A.
Precipitation changes the physical and biological characteristics of an ecosystem. Using a precipitation-based conditional sampling technique and a 14 year data set from a 25 m micrometeorological tower in a high-elevation subalpine forest, we examined how warm-season precipitation affected the above-canopy diel cycle of wind and turbulence, net radiation R net, ecosystem eddy covariance fluxes (sensible heat H, latent heat LE, and CO 2 net ecosystem exchange NEE) and vertical profiles of scalars (air temperature T a, specific humidity q, and CO 2 dry mole fraction χ c). This analysis allowed us to examine how precipitation modified these variables frommore » hourly (i.e., the diel cycle) to multi-day time-scales (i.e., typical of a weather-system frontal passage). During mid-day we found the following: (i) even though precipitation caused mean changes on the order of 50–70 % to R net, H, and LE, the surface energy balance (SEB) was relatively insensitive to precipitation with mid-day closure values ranging between 90 and 110 %, and (ii) compared to a typical dry day, a day following a rainy day was characterized by increased ecosystem uptake of CO 2 (NEE increased by ≈ 10 %), enhanced evaporative cooling (mid-day LE increased by ≈ 30 W m –2), and a smaller amount of sensible heat transfer (mid-day H decreased by ≈ 70 W m –2). Based on the mean diel cycle, the evaporative contribution to total evapotranspiration was, on average, around 6 % in dry conditions and between 15 and 25 % in partially wet conditions. Furthermore, increased LE lasted at least 18 h following a rain event. At night, even though precipitation (and accompanying clouds) reduced the magnitude of R net, LE increased from ≈ 10 to over 20 W m –2 due to increased evaporation. Any effect of precipitation on the nocturnal SEB closure and NEE was overshadowed by atmospheric phenomena such as horizontal advection and decoupling that create measurement difficulties. Above-canopy mean χ c during wet conditions was found to be about 2–3 μmol mol –1 larger than χ c on dry days. This difference was fairly constant over the full diel cycle suggesting that it was due to synoptic weather patterns (different air masses and/or effects of barometric pressure). Lastly, the effect of clouds on the timing and magnitude of daytime ecosystem fluxes is described.« less
Diel behavior of rare earth elements in a mountain stream with acidic to neutral pH
Gammons, C.H.; Wood, S.A.; Nimick, D.A.
2005-01-01
Diel (24-h) changes in concentrations of rare earth elements (REE) were investigated in Fisher Creek, a mountain stream in Montana that receives acid mine drainage in its headwaters. Three simultaneous 24-h samplings were conducted at an upstream station (pH = 3.3), an intermediate station (pH = 5.5), and a downstream station (pH = 6.8). The REE were found to behave conservatively at the two upstream stations. At the downstream station, REE partitioned into suspended particles to a degree that varied with the time of day, and concentrations of dissolved REE were 2.9- to 9.4-fold (190% to 830%) higher in the early morning vs. the late afternoon. The decrease in dissolved REE concentrations during the day coincided with a corresponding increase in the concentration of REE in suspended particles, such that diel changes in the total REE concentrations were relatively minor (27% to 55% increase at night). Across the lanthanide series, the heavy REE partitioned into the suspended solid phase to a greater extent than the light REE. Filtered samples from the downstream station showed a decrease in shale-normalized REE concentration across the lanthanide series, with positive anomalies at La and Gd, and a negative Eu anomaly. As the temperature of the creek increased in the afternoon, the slope of the REE profile steepened and the magnitude of the anomalies increased. The above observations are explained by cyclic adsorption of REE onto suspended particles of hydrous ferric and aluminum oxides (HFO, HAO). Conditional partition coefficients for each REE between the suspended solids and the aqueous phase reached a maximum at 1700 hours and a minimum at 0700 hours. This pattern is attributed to diel variations in stream temperature, possibly reinforced by kinetic factors (i.e., slower rates of reaction at night than during the day). Estimates of the enthalpy of adsorption of each REE onto suspended particles based on the field results averaged +82 kJ/mol and are similar in magnitude to estimates in the literature for adsorption of divalent metal cations onto clays and hydrous metal oxides. The results of this study have important implications to the use of REE as hydrogeochemical tracers in streams. Copyright ?? 2005 Elsevier Ltd.
Vegetation induced diel signal and its meaning in recharge and discharge regions
NASA Astrophysics Data System (ADS)
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 water table or soil moisture measurements can only be achieved by understanding the different hydrological characteristics of recharge and discharge zones. In the context of climate change higher temperature and longer dry periods induced higher evapotranspiration constrain will probably reduce the groundwater level and so the spatial extent of shallow groundwater areas (reachable groundwater resources for vegetation). Therefore the better understanding of hydrological impact of different surface covers in shallow groundwater areas in changing climate is crucial, not only from water resources management point of view, but also from the viewpoint of agricultural and forest production or survival of forests with high water demand. This research has been mainly supported by the Agroclimate.2 VKSZ_12-1-2013-0034 project. The research of Zoltán Gribovszki was supported by the European Union and the State of Hungary, co-financed by the European Social Fund in the framework of TÁMOP 4.2.4. A/2-11-1-2012-0001 'National Excellence Program'.
Flores, Beatris; Molinski, Tadeusz F.
2011-01-01
The hexahydro-1H-isoindolin-1-one core of muironolide A was prepared by asymmetric intramolecular Diels Alder cycloaddition using a variant of the MacMillan organocatalyst which sets the C4,C5 and C11 stereocenters. PMID:21751773
A microwave assisted intramolecular-furan-Diels-Alder approach to 4-substituted indoles.
Petronijevic, Filip; Timmons, Cody; Cuzzupe, Anthony; Wipf, Peter
2009-01-07
The key steps of a versatile new protocol for the convergent synthesis of 3,4-disubstituted indoles are the addition of an alpha-lithiated alkylaminofuran to a carbonyl compound, a microwave-accelerated intramolecular Diels-Alder cycloaddition and an in situ double aromatization reaction.
Diel variability of mercury phase and species distributions in the Florida Everglades
Krabbenhoft, D.P.; Hurley, J.P.; Olson, M.L.; Cleckner, L.B.
1998-01-01
Preliminary studies of mercury (Hg) cycling in the Everglades revealed that dissolved gaseous mercury (DGM), total mercury (Hg(T)), and reactive mercury (Hg(R)) show reproducible, diel trends. Peak water-column DGM concentrations were observed on or about noon, with a 3 to 7 fold increase over night-time concentrations. Production of DGM appears to cease during dark periods, with nearly constant water column concentrations that were at or near saturation with respect to the overlying air. A simple mass balance shows that the flux of Hg to the atmosphere from diel DGM production and evasion represents about 10% of the annual input from atmospheric deposition. Production of DGM is likely the result of an indirect photolysis reaction that involves the production of reductive species and/or reduction by electron transfer. Diel variability in Hg(T) and Hg(R) appears to be controlled by two factors: inputs from rainfall and photolytic sorption/desorption processes. A possible mechanism involves photolysis of chromophores on the surface of a solid substrate (e.g., the periphyton mat) giving rise to destabilization of sorbed mercury and net desorption during daylight. At night, the sorption reactions predominate and the water-column Hg(T) decreases. Methylmercury (MeHg) also showed diel trends in concentration but were not clearly linked to the solar cycle or rainfall at the study site.
Bowling, D. R.; Egan, J. E.; Hall, S. J.; ...
2015-08-31
Recent studies have examined temporal fluctuations in the amount and carbon isotope content (δ 13C) of CO 2 produced by the respiration of roots and soil organisms. These changes have been correlated with diel cycles of environmental forcing (e.g., sunlight and soil temperature) and with synoptic-scale atmospheric motion (e.g., rain events and pressure-induced ventilation). We used an extensive suite of measurements to examine soil respiration over 2 months in a subalpine forest in Colorado, USA (the Niwot Ridge AmeriFlux forest). Observations included automated measurements of CO 2 and δ 13C of CO 2 in the soil efflux, the soil gasmore » profile, and forest air. There was strong diel variability in soil efflux but no diel change in the δ 13C of the soil efflux (δ R) or the CO 2 produced by biological activity in the soil (δ J). Following rain, soil efflux increased significantly, but δ R and δ J did not change. Temporal variation in the δ 13C of the soil efflux was unrelated to measured environmental variables, and we failed to find an explanation for this unexpected result. Measurements of the δ 13C of the soil efflux with chambers agreed closely with independent observations of the isotopic composition of soil CO 2 production derived from soil gas well measurements. Deeper in the soil profile and at the soil surface, results confirmed established theory regarding diffusive soil gas transport and isotopic fractionation. Deviation from best-fit diffusion model results at the shallower depths illuminated a pump-induced ventilation artifact that should be anticipated and avoided in future studies. There was no evidence of natural pressure-induced ventilation of the deep soil. However, higher variability in δ 13C of the soil efflux relative to δ 13C of production derived from soil profile measurements was likely caused by transient pressure-induced transport with small horizontal length scales.« less
NASA Astrophysics Data System (ADS)
Song, W.; Staudt, M.; Bourgeois, I.; Williams, J.
2013-10-01
Plants emit significant amounts of monoterpenes into the Earth's atmosphere where they react rapidly to form a multitude of gas phase species and particles. Many monoterpenes exist in mirror images forms or enantiomers. In this study the enantiomeric monoterpene profile for several representative plants (Quercus ilex L., Rosmarinus officinalis L., and Pinus halepensis Mill.) was investigated as a function of chemotype, light and temperature both in the laboratory and in the field. Analysis of enantiomeric monoterpenes from 19 Quercus ilex individuals from Southern France and Spain revealed four regiospecific chemotypes (genetically fixed emission patterns). In agreement with previous work, only Quercus ilex emissions increased strongly with light. However, for all three plant species no consistent enantiomeric variation was observed as a function of light, and the enantiomeric ratio of α-pinene was found vary by less than 20% from 100 and 1000 μmol m-2 s-1 PAR. The rate of monoterpene emission increased with temperature from all three plant species, but little variation in the enantiomeric distribution of α-pinene was observed with temperature. There was more enantiomeric variability between individuals of the same species than could be induced by either light or temperature. Field measurements of α-pinene enantiomer mixing ratios in the air taken at a Quercus ilex forest in Southern France, and several other previously reported field enantiomeric ratio diel cycle profiles are compared. All show smoothly varying diel cycles (some positive and some negative) even over changing wind directions. This is surprising in comparison with variations of enantiomeric emission patterns shown by individuals of the same species.
Hunting influences the diel patterns in habitat selection by northern pintails Anas acuta
Casazza, Michael L.; Coates, Peter S.; Miller, Michael R.; Overton, Cory T.; Yparraguirre, Daniel R.
2012-01-01
Northern pintail Anas acuta (hereafter pintail) populations wintering within Suisun Marsh, a large estuarine managed wetland near San Francisco Bay, California,USA, have declined markedly over the last four decades. The reasons for this decline are unclear. Information on how hunting and other factors influence the selection of vegetation types and sanctuaries would be beneficial to manage pintail populations in SuisunMarsh. During 1991-1993, we radio-marked and relocated female pintails (individuals: N = 203, relocations: N = 7,688) within Suisun Marsh to investigate habitat selection during the non-breeding months (winter). We calculated selection ratios for different vegetation types and for sanctuaries, and examined differences in those ratios between hunting season (i.e. hunting and non-hunting), age (hatchyear and after-hatch-year), and time of day (daylight or night hours). We found that diel patterns in selection were influenced by hunting disturbance. For example, prior to the hunting season and during daylight hours, pintails selected areas dominated by brass buttons Cotula coronopifolia, a potentially important food source, usually outside of sanctuary boundaries. However, during the hunting season, pintails did not select brass buttons during daylight hours, but instead highly selected permanent pools, mostly within sanctuaries. Also, during the hunting season, pintails showed strong selection for brass buttons at night. Sanctuaries provided more area of permanent water pools than within hunting areas and appeared to function as important refugia during daylight hours of the hunting season. Wildlife managers should encourage large protected permanent pools adjacent to hunted wetlands to increase pintail numbers within wetland environments and responsibly benefit hunting opportunities while improving pintail conservation.
Stiffler, Lydia L.; Anderson, James T.; Welsh, Amy B.; Harding, Sergio R.; Costanzo, Gary R.; Katzner, Todd
2017-01-01
Surveys for secretive marsh birds could be improved with refinements to address regional and species-specific variation in detection probabilities and optimal times of day to survey. Diel variation in relation to naïve occupancy, detection rates, and vocalization rates of King (Rallus elegans) and Clapper (R. crepitans) rails were studied in intracoastal waterways in Virginia, USA. Autonomous acoustic devices recorded vocalizations of King and Clapper rails at 75 locations for 48-hr periods within a marsh complex. Naïve King and Clapper rail occupancy did not vary hourly at either the marsh or the study area level. Combined King and Clapper rail detections and vocalizations varied across marshes, decreased as the sampling season progressed, and, for detections, was greatest during low rising tides (P < 0.01). Hourly variation in vocalization and detection rates did not show a pattern but occurred between 7.8% of pairwise comparisons for detections and 10.5% of pairwise comparisons for vocalizations (P < 0.01). Higher rates of detections and vocalizations occurred during the hours of 00:00–00:59, 05:00–05:59, 14:00–15:59, and lower rates during the hours of 07:00–09:59. Although statistically significant, because there were no patterns in these hourly differences, they may not be biologically relevant and are of little use to management. In fact, these findings demonstrate that surveys for King and Clapper rails in Virginia intracoastal waterways may be effectively conducted throughout the day.
Nitrogen Fixation (Acetylene Reduction) by Epiphytes of Freshwater Macrophytes
Finke, Linda R.; Seeley, H. W.
1978-01-01
The involvement of epiphytic microorganisms in nitrogen fixation was investigated in a shallow freshwater pond near Ithaca, N.Y. The acetylene reduction technique was used to follow diel and seasonal cycles of nitrogen fixation by epiphytes of Myriophyllum spicatum. Acetylene-reducing activity was maximal between noon and 6 p.m., but substantial levels of activity relative to daytime rates continued through the night. Experiments with the seasonal course of activity showed a gradual decline during the autumn months and no activity in January or February. Activity commenced in May, with an abrupt increase to levels between 0.45 and 0.95 nmol of ethylene formed per mg (dry weight) of plant per h. Through most of the summer months, mean rates of acetylene reduction remained between 0.15 and 0.60 nmol/mg (dry weight) per h. It was calculated from diel and seasonal cycles that, in the pond areas studied, epiphytes were capable of adding from 7.5 to 12.5 μg of N per mg of plant per year to the pond. This amount is significant relative to the total amount of nitrogen incorporated into the plant. Blue-green algae (cyanobacteria), particularly Gloeotrichia, appeared to bear prime responsibility for nitrogen fixation, but photosynthetic bacteria of the genus Rhodopseudomonas were isolated from M. spicatum and shown to support high rates of acetylene reduction. PMID:16345301
NASA Astrophysics Data System (ADS)
Cook, April B.; Sutton, Tracey T.; Galbraith, John K.; Vecchione, Michael
2013-12-01
Only a miniscule fraction of the world’s largest volume of living space, the ocean’s midwater biome, has ever been sampled. As part of the International Census of Marine Life field project on Mid-Atlantic Ridge ecosystems (MAR-ECO), a discrete-depth trawling survey was conducted in 2009 aboard the NOAA FSV Henry B. Bigelow to examine the pelagic faunal assemblage structure and distribution over the Charlie-Gibbs Fracture Zone (CGFZ) of the northern Mid-Atlantic Ridge. Day/night sampling at closely spaced stations allowed the first characterization of diel vertical migration of pelagic nekton over the MAR-ECO study area. Discrete-depth sampling from 0-3000 m was conducted using a Norwegian “Krill” trawl with five codends that were opened and closed via a pre-programmed timer. Seventy-five species of fish were collected, with a maximum diversity and biomass observed between depths of 700-1900 m. A gradient in sea-surface temperature and underlying watermasses, from northwest to southeast, was mirrored by a similar gradient in ichthyofaunal diversity. Using multivariate analyses, eight deep-pelagic fish assemblages were identified, with depth as the primary discriminatory variable. Strong diel vertical migration (DVM) of the mesopelagic fauna was a prevalent feature of the study area, though the numerically dominant fish, Cyclothone microdon (Gonostomatidae), exhibited a broad (0-3000 m) vertical distribution and did not appear to migrate on a diel basis. Three patterns of vertical distribution were observed in the study area: (a) DVM of mesopelagic, and possibly bathypelagic, taxa; (b) broad vertical distribution spanning meso- and bathypelagic depths; and (c) discrete vertical distribution within a limited depth range. Overall species composition and rank order of abundance of fish species agreed with two previous expeditions to the CGFZ (1982-1983 and 2004), suggesting some long-term consistency in the ichthyofaunal composition of the study area, at least in the summer. Frequent captures of putative bathypelagic fishes, shrimps, and cephalopods in the epipelagic zone (0-200 m) were confirmed. The results of this expedition reveal distributional patterns unlike those previously reported for open-ocean ecosystems, with the implication of increased transfer efficiency of surface production to great depths in the mid-North Atlantic.
USDA-ARS?s Scientific Manuscript database
Angelica sinensis (Oliv.) Diels (“Danggui” in Chinese) is one of the most commonly used Traditional Chinese Medicines (TCMs). It has been used to invigorate blood circulation for the treatment of anemia, hypertension, chronic bronchitis, asthma, rheumatism and cardiovascular diseases. There are a lo...
The Diels-Alder cyclization of ketenimines.
Erb, Jeremy; Strull, Jessica; Miller, David; He, Jean; Lectka, Thomas
2012-04-20
A Diels-Alder reaction between cyclopentadiene and a variety of ketenimines is reported. A copper(I)-bis(phosphine complex catalyzes the cycloaddition across the C═N bond of the ketenimine in a [4 + 2] reaction to give an enamine intermediate that is hydrolyzed upon purification to generate aminoketones. © 2012 American Chemical Society
Hutchins, David A.; Walworth, Nathan G.; Webb, Eric A.; Saito, Mak A.; Moran, Dawn; McIlvin, Matthew R.; Gale, Jasmine; Fu, Fei-Xue
2015-01-01
Nitrogen fixation rates of the globally distributed, biogeochemically important marine cyanobacterium Trichodesmium increase under high carbon dioxide (CO2) levels in short-term studies due to physiological plasticity. However, its long-term adaptive responses to ongoing anthropogenic CO2 increases are unknown. Here we show that experimental evolution under extended selection at projected future elevated CO2 levels results in irreversible, large increases in nitrogen fixation and growth rates, even after being moved back to lower present day CO2 levels for hundreds of generations. This represents an unprecedented microbial evolutionary response, as reproductive fitness increases acquired in the selection environment are maintained after returning to the ancestral environment. Constitutive rate increases are accompanied by irreversible shifts in diel nitrogen fixation patterns, and increased activity of a potentially regulatory DNA methyltransferase enzyme. High CO2-selected cell lines also exhibit increased phosphorus-limited growth rates, suggesting a potential advantage for this keystone organism in a more nutrient-limited, acidified future ocean. PMID:26327191
NASA Astrophysics Data System (ADS)
Hutchins, David A.; Walworth, Nathan G.; Webb, Eric A.; Saito, Mak A.; Moran, Dawn; McIlvin, Matthew R.; Gale, Jasmine; Fu, Fei-Xue
2015-09-01
Nitrogen fixation rates of the globally distributed, biogeochemically important marine cyanobacterium Trichodesmium increase under high carbon dioxide (CO2) levels in short-term studies due to physiological plasticity. However, its long-term adaptive responses to ongoing anthropogenic CO2 increases are unknown. Here we show that experimental evolution under extended selection at projected future elevated CO2 levels results in irreversible, large increases in nitrogen fixation and growth rates, even after being moved back to lower present day CO2 levels for hundreds of generations. This represents an unprecedented microbial evolutionary response, as reproductive fitness increases acquired in the selection environment are maintained after returning to the ancestral environment. Constitutive rate increases are accompanied by irreversible shifts in diel nitrogen fixation patterns, and increased activity of a potentially regulatory DNA methyltransferase enzyme. High CO2-selected cell lines also exhibit increased phosphorus-limited growth rates, suggesting a potential advantage for this keystone organism in a more nutrient-limited, acidified future ocean.
Johnson, J. H.; Nack, C.C.
2010-01-01
We examined feeding periodicity of three size groups of the rusty crayfish (Orconectes rusticus) at four-hour intervals over a 28-hour period during July in a headwater stream of the Susquehanna River drainage in central New York. Feeding activity was expressed as the ratio of stomach weight divided by the crayfish wet weight. The diel food consumption patterns of all three size groups of rusty crayfish (i.e., ??? 10 mm, 11-20 mm, and > 20 mm carapace length) were significantly different. Peak feeding of the smallest crayfish occurred during crepuscular periods. Food consumption of the intermediate size crayfish was highest at 2000 h, and feeding of large crayfish was consistently high from 1200 h to 0400 h. Feeding intensity of both small and intermediate size crayfish was highest when feeding intensity of large crayfsh was lowest. Ontogenetic differences in feeding periodicity may be associated with predation pressure from large rusty crayfish on smaller individuals.
Johnson, James H.; Nack, Christopher C.
2010-01-01
We examined feeding periodicity of three size groups of the rusty crayfish (Orconectes rusticus) at four-hour intervals over a 28-hour period during July in a headwater stream of the Susquehanna River drainage in central New York. Feeding activity was expressed as the ratio of stomach weight divided by the crayfish wet weight. The diel food consumption patterns of all three size groups of rusty crayfish (i.e., ≤ 10 mm, 11–20 mm, and > 20 mm carapace length) were significantly different. Peak feeding of the smallest crayfish occurred during crepuscular periods. Food consumption of the intermediate size crayfish was highest at 2000 h, and feeding of large crayfish was consistently high from 1200 h to 0400 h. Feeding intensity of both small and intermediate size crayfish was highest when feeding intensity of large crayfsh was lowest. Ontogenetic differences in feeding periodicity may be associated with predation pressure from large rusty crayfish on smaller individuals.
NASA Astrophysics Data System (ADS)
Rivero, Uxía; Meuwly, Markus; Willitsch, Stefan
2017-09-01
The neutral and cationic Diels-Alder-type reactions between 2,3-dibromo-1,3-butadiene and maleic anhydride have been computationally explored as the first step of a combined experimental and theoretical study. Density functional theory calculations show that the neutral reaction is concerted while the cationic reaction can be either concerted or stepwise. Further isomerizations of the Diels-Alder products have been studied in order to predict possible fragmentation pathways in gas-phase experiments. Rice-Ramsperger-Kassel-Marcus (RRKM) calculations suggest that under single-collision experimental conditions the neutral product may reform the reactants and the cationic product will most likely eliminate CO2.
NASA Astrophysics Data System (ADS)
Mancini, Pedro M. E.; Kneeteman, María N.; Cainelli, Mauro; Ormachea, Carla M.; Domingo, Luis R.
2017-11-01
The behaviors of N-tosylnitropyrroles acting as electrophilic dienophiles in polar Diels-Alder reactions joint to different dienes of increeased nucleophilicity are analyzed. The reactions were developed under microwave irradiation using toluene or protic ionic liquids (PILs) as solvents and in free solvent conditions. In all the cases explored we observed good yields in short reaction times. For these reactions, the free solvent condition and the use of protic ionic liquids as solvents offer similar results. However, the free solvent conditions favor environmental sustainability. The role of PILs in these polar Diels-Alder reactions has been theoretically studied within the Molecular Electron Density Theory.
Tandem enyne metathesis-Diels-Alder reaction for construction of natural product frameworks.
Rosillo, Marta; Domínguez, Gema; Casarrubios, Luis; Amador, Ulises; Pérez-Castells, Javier
2004-03-19
Enynes connected through aromatic rings are used as substrates for metathesis reactions. The reactivity of three ruthenium carbene complexes is compared. The resulting 1,3-dienes are suitable precursors of polycyclic structures via a Diels-Alder process. Some domino RCM-Diels-Alder reactions are performed, suggesting a possible beneficial effect of the ruthenium catalyst in the cycloaddition process. Other examples require Lewis acid cocatalyst. When applied to aromatic ynamines or enamines, a new synthesis of vinylindoles is achieved. Monitorization of several metathesis reactions with NMR shows the different behavior for ruthenium catalysts. New carbenic species are detected in some reactions with an important dependence on the solvent used.
The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...
Interpreting diel hysteresis between soil respiration and temperature
C. Phillips; N. Nickerson; D. Risk; B.J. Bond
2011-01-01
Increasing use of automated soil respiration chambers in recent years has demonstrated complex diel relationships between soil respiration and temperature that are not apparent from less frequent measurements. Soil surface flux is often lagged from soil temperature by several hours, which results in semielliptical hysteresis loops when surface flux is plotted as a...
Diel and seasonal variation in food habits of Atlantic salmon parr in a small stream
Grader, M.; Letcher, B.H.
2006-01-01
The diel and seasonal food habits of young-of-year (YOY) and post-young-of-year (PYOY) Atlantic salmon (Salmo salar) parr were assayed over the course of 11 months in the West Brook, Massachusetts USA. Gut fullness of YOY salmon did not vary significantly among months. PYOY salmon exhibited significant seasonal differences in gut fullness, with peak fullness occurring in the spring and late fall. Significant diel differences in PYOY gut fullness occurred in June and April, with peak fullness always occurring at dawn. Prey composition varied substantially among months. Dominant prey items of PYOY salmon were baetid mayflies in June, July, and August, limnephilid caddisflies in October and November, and ephemerellid mayflies in February and April. Few differences in prey composition between PYOY and YOY salmon were observed. Fish growth was unrelated to prey availability, but gut fullness explained up to 97% of growth variation across seasons. Results suggest that spring and fall are critical periods of feeding for PYOY salmon and that diel feeding intensity shifts seasonally.
Wilson, Samuel T; Aylward, Frank O; Ribalet, Francois; Barone, Benedetto; Casey, John R; Connell, Paige E; Eppley, John M; Ferrón, Sara; Fitzsimmons, Jessica N; Hayes, Christopher T; Romano, Anna E; Turk-Kubo, Kendra A; Vislova, Alice; Armbrust, E Virginia; Caron, David A; Church, Matthew J; Zehr, Jonathan P; Karl, David M; DeLong, Edward F
2017-07-31
The temporal dynamics of phytoplankton growth and activity have large impacts on fluxes of matter and energy, yet obtaining in situ metabolic measurements of sufficient resolution for even dominant microorganisms remains a considerable challenge. We performed Lagrangian diel sampling with synoptic measurements of population abundances, dinitrogen (N 2 ) fixation, mortality, productivity, export and transcription in a bloom of Crocosphaera over eight days in the North Pacific Subtropical Gyre (NPSG). Quantitative transcriptomic analyses revealed clear diel oscillations in transcript abundances for 34% of Crocosphaera genes identified, reflecting a systematic progression of gene expression in diverse metabolic pathways. Significant time-lagged correspondence was evident between nifH transcript abundance and maximal N 2 fixation, as well as sepF transcript abundance and cell division, demonstrating the utility of transcriptomics to predict the occurrence and timing of physiological and biogeochemical processes in natural populations. Indirect estimates of carbon fixation by Crocosphaera were equivalent to 11% of net community production, suggesting that under bloom conditions this diazotroph has a considerable impact on the wider carbon cycle. Our cross-scale synthesis of molecular, population and community-wide data underscores the tightly coordinated in situ metabolism of the keystone N 2 -fixing cyanobacterium Crocosphaera, as well as the broader ecosystem-wide implications of its activities.
Nifong, James C.; Nifong, Rachel L.; Silliman, Brian R.; Lowers, Russell H.; Guillette, Louis J.; Ferguson, Jake M.; Welsh, Matthew; Abernathy, Kyler; Marshall, Greg
2014-01-01
Large-bodied, top- and apex predators (e.g., crocodilians, sharks, wolves, killer whales) can exert strong top-down effects within ecological communities through their interactions with prey. Due to inherent difficulties while studying the behavior of these often dangerous predatory species, relatively little is known regarding their feeding behaviors and activity patterns, information that is essential to understanding their role in regulating food web dynamics and ecological processes. Here we use animal-borne imaging systems (Crittercam) to study the foraging behavior and activity patterns of a cryptic, large-bodied predator, the American alligator (Alligator mississippiensis) in two estuaries of coastal Florida, USA. Using retrieved video data we examine the variation in foraging behaviors and activity patterns due to abiotic factors. We found the frequency of prey-attacks (mean = 0.49 prey attacks/hour) as well as the probability of prey-capture success (mean = 0.52 per attack) were significantly affected by time of day. Alligators attempted to capture prey most frequently during the night. Probability of prey-capture success per attack was highest during morning hours and sequentially lower during day, night, and sunset, respectively. Position in the water column also significantly affected prey-capture success, as individuals’ experienced two-fold greater success when attacking prey while submerged. These estimates are the first for wild adult American alligators and one of the few examples for any crocodilian species worldwide. More broadly, these results reveal that our understandings of crocodilian foraging behaviors are biased due to previous studies containing limited observations of cryptic and nocturnal foraging interactions. Our results can be used to inform greater understanding regarding the top-down effects of American alligators in estuarine food webs. Additionally, our results highlight the importance and power of using animal-borne imaging when studying the behavior of elusive large-bodied, apex predators, as it provides critical insights into their trophic and behavioral interactions. PMID:24454711
Nifong, James C; Nifong, Rachel L; Silliman, Brian R; Lowers, Russell H; Guillette, Louis J; Ferguson, Jake M; Welsh, Matthew; Abernathy, Kyler; Marshall, Greg
2014-01-01
Large-bodied, top- and apex predators (e.g., crocodilians, sharks, wolves, killer whales) can exert strong top-down effects within ecological communities through their interactions with prey. Due to inherent difficulties while studying the behavior of these often dangerous predatory species, relatively little is known regarding their feeding behaviors and activity patterns, information that is essential to understanding their role in regulating food web dynamics and ecological processes. Here we use animal-borne imaging systems (Crittercam) to study the foraging behavior and activity patterns of a cryptic, large-bodied predator, the American alligator (Alligator mississippiensis) in two estuaries of coastal Florida, USA. Using retrieved video data we examine the variation in foraging behaviors and activity patterns due to abiotic factors. We found the frequency of prey-attacks (mean = 0.49 prey attacks/hour) as well as the probability of prey-capture success (mean = 0.52 per attack) were significantly affected by time of day. Alligators attempted to capture prey most frequently during the night. Probability of prey-capture success per attack was highest during morning hours and sequentially lower during day, night, and sunset, respectively. Position in the water column also significantly affected prey-capture success, as individuals' experienced two-fold greater success when attacking prey while submerged. These estimates are the first for wild adult American alligators and one of the few examples for any crocodilian species worldwide. More broadly, these results reveal that our understandings of crocodilian foraging behaviors are biased due to previous studies containing limited observations of cryptic and nocturnal foraging interactions. Our results can be used to inform greater understanding regarding the top-down effects of American alligators in estuarine food webs. Additionally, our results highlight the importance and power of using animal-borne imaging when studying the behavior of elusive large-bodied, apex predators, as it provides critical insights into their trophic and behavioral interactions.
Aspillaga, Eneko; Bartumeus, Frederic; Linares, Cristina; Starr, Richard M; López-Sanz, Àngel; Díaz, David; Zabala, Mikel; Hereu, Bernat
2016-01-01
It is important to account for the movement behaviour of fishes when designing effective marine protected areas (MPAs). Fish movements occur across different spatial and temporal scales and understanding the variety of movements is essential to make correct management decisions. This study describes in detail the movement patterns of an economically and commercially important species, Diplodus sargus, within a well-enforced Mediterranean MPA. We monitored horizontal and vertical movements of 41 adult individuals using passive acoustic telemetry for up to one year. We applied novel analysis and visualization techniques to get a comprehensive view of a wide range of movements. D. sargus individuals were highly territorial, moving within small home ranges (< 1 km2), inside which they displayed repetitive diel activity patterns. Extraordinary movements beyond the ordinary home range were observed under two specific conditions. First, during stormy events D. sargus presented a sheltering behaviour, moving to more protected places to avoid the disturbance. Second, during the spawning season they made excursions to deep areas (> 50 m), where they aggregated to spawn. This study advances our understanding about the functioning of an established MPA and provides important insights into the biology and management of a small sedentary species, suggesting the relevance of rare but important fish behaviours.
Aspillaga, Eneko; Bartumeus, Frederic; Linares, Cristina; Starr, Richard M.; López-Sanz, Àngel; Díaz, David; Zabala, Mikel; Hereu, Bernat
2016-01-01
It is important to account for the movement behaviour of fishes when designing effective marine protected areas (MPAs). Fish movements occur across different spatial and temporal scales and understanding the variety of movements is essential to make correct management decisions. This study describes in detail the movement patterns of an economically and commercially important species, Diplodus sargus, within a well-enforced Mediterranean MPA. We monitored horizontal and vertical movements of 41 adult individuals using passive acoustic telemetry for up to one year. We applied novel analysis and visualization techniques to get a comprehensive view of a wide range of movements. D. sargus individuals were highly territorial, moving within small home ranges (< 1 km2), inside which they displayed repetitive diel activity patterns. Extraordinary movements beyond the ordinary home range were observed under two specific conditions. First, during stormy events D. sargus presented a sheltering behaviour, moving to more protected places to avoid the disturbance. Second, during the spawning season they made excursions to deep areas (> 50 m), where they aggregated to spawn. This study advances our understanding about the functioning of an established MPA and provides important insights into the biology and management of a small sedentary species, suggesting the relevance of rare but important fish behaviours. PMID:27437692
Invasive fishes generate biogeochemical hotspots in a nutrient-limited system.
Capps, Krista A; Flecker, Alexander S
2013-01-01
Fishes can play important functional roles in the nutrient dynamics of freshwater systems. Aggregating fishes have the potential to generate areas of increased biogeochemical activity, or hotspots, in streams and rivers. Many of the studies documenting the functional role of fishes in nutrient dynamics have focused on native fish species; however, introduced fishes may restructure nutrient storage and cycling freshwater systems as they can attain high population densities in novel environments. The purpose of this study was to examine the impact of a non-native catfish (Loricariidae: Pterygoplichthys) on nitrogen and phosphorus remineralization and estimate whether large aggregations of these fish generate measurable biogeochemical hotspots within nutrient-limited ecosystems. Loricariids formed large aggregations during daylight hours and dispersed throughout the stream during evening hours to graze benthic habitats. Excretion rates of phosphorus were twice as great during nighttime hours when fishes were actively feeding; however, there was no diel pattern in nitrogen excretion rates. Our results indicate that spatially heterogeneous aggregations of loricariids can significantly elevate dissolved nutrient concentrations via excretion relative to ambient nitrogen and phosphorus concentrations during daylight hours, creating biogeochemical hotspots and potentially altering nutrient dynamics in invaded systems.
Invasive Fishes Generate Biogeochemical Hotspots in a Nutrient-Limited System
Capps, Krista A.; Flecker, Alexander S.
2013-01-01
Fishes can play important functional roles in the nutrient dynamics of freshwater systems. Aggregating fishes have the potential to generate areas of increased biogeochemical activity, or hotspots, in streams and rivers. Many of the studies documenting the functional role of fishes in nutrient dynamics have focused on native fish species; however, introduced fishes may restructure nutrient storage and cycling freshwater systems as they can attain high population densities in novel environments. The purpose of this study was to examine the impact of a non-native catfish (Loricariidae: Pterygoplichthys) on nitrogen and phosphorus remineralization and estimate whether large aggregations of these fish generate measurable biogeochemical hotspots within nutrient-limited ecosystems. Loricariids formed large aggregations during daylight hours and dispersed throughout the stream during evening hours to graze benthic habitats. Excretion rates of phosphorus were twice as great during nighttime hours when fishes were actively feeding; however, there was no diel pattern in nitrogen excretion rates. Our results indicate that spatially heterogeneous aggregations of loricariids can significantly elevate dissolved nutrient concentrations via excretion relative to ambient nitrogen and phosphorus concentrations during daylight hours, creating biogeochemical hotspots and potentially altering nutrient dynamics in invaded systems. PMID:23342083
Xin, Danhui; Hao, Yongxia; Shimaoka, Takayuki; Nakayama, Hirofumi; Chai, Xiaoli
2016-11-01
Diel methane emission fluxes from a landfill that was covered by vegetation were investigated to reveal the methane emission mechanisms based on the interaction of vegetation characteristics and climate factors. The methane emissions showed large variation between daytime and nighttime, and the trend of methane emissions exhibited clear bimodal patterns from both Setaria viridis- and Neyraudia reynaudiana-covered areas. Plants play an important role in methane transportation as well as methane oxidation. The notable decrease in methane emissions after plants were cut suggests that methane transportation via plants is the primary way of methane emissions in the vegetated areas of landfill. Within plants, the methane emission fluxes were enhanced due to a convection mechanism. Given that the methane emission flux is highly correlated with the solar radiation during daytime, the convection mechanism could be attributed to the increase in solar radiation. Whereas the methane emission flux is affected by a combined impact of the wind speed and pedosphere characteristics during nighttime. An improved understanding of the methane emission mechanisms in vegetated landfills is expected to develop a reliable model for landfill methane emissions and to attenuate greenhouse gas emissions from landfills. Copyright © 2016 Elsevier Ltd. All rights reserved.
Suzuki, F. M.; Dunham, Jason B.; Silva, L. G. M.; Alves, C. B. M.; Pompeu, P.S.
2017-01-01
Fish attempting to move upstream through hydroelectric dams can be trapped and killed in turbines. Understanding fish movement patterns can provide useful insights for how to manage dam operations to minimize fish kill in turbines. We evaluated the movements of two migratory fish (Curimba-Prochilodus argenteus and Mandi-Pimelodus maculatus) using acoustic telemetry in the tailrace of Três Marias Dam (São Francisco River, Brazil) from 31 October 2011 to 16 February 2012. The majority of tagged fish left the tailrace in less than one week; however, some individuals returned, performing several visits to the tailrace. Mandi remained longer in the tailrace than Curimba. The number of visits was influenced by diel period, turbine and spillway discharge. Although the diel period was the only important contributor to the visits performed by Curimba, the movements of Mandi were significantly influenced by three factors. We found that whereas Curimba was predominantly diurnal, Mandi showed nocturnal habits. Additionally, visits of Mandi were significantly greater during higher turbine and spillway discharge. We discuss the implications of these results for understanding fish movements in the Três Marias Dam tailrace and their potential implications for adapting hydroelectric operations to minimize fish kills.
NASA Astrophysics Data System (ADS)
Primo, Ana Lígia; Azeiteiro, Ulisses M.; Marques, Sónia C.; Martinho, Filipe; Baptista, Joana; Pardal, Miguel A.
2013-02-01
Migrations between coastal and estuarine nursery areas are essential for successful completion of the life cycle of several marine fish. The present study evaluates the use of a small temperate estuary, the Mondego, Portugal, as a nursery habitat for several flatfishes during their early life stages. Data from seasonal and diel larval sampling at the mouth of the estuary and both larvae and juvenile monthly spatial distribution in the estuary (2005-2009) were gathered in order to investigate the life cycle of Platichthys flesus, Solea solea and Solea senegalensis. Larvae entrance in the estuary occurred mainly during summer and autumn with no evidence for diel or tidal vertical stratification. S. senegalensis larvae were present in all seasons at downstream areas presenting low successful settlement and juveniles' densities inside the estuary. Conversely, P. flesus and S. solea were mainly present as juveniles with upstream areas being preferred by flounder. Both species larvae seemed to settle in nearby coastal areas. The importance of the Mondego estuary for flatfishes differed according to the species, playing an important role mainly during the first year for all species. The present study highlights the importance of integrating larval and juvenile stages of fish to assess the very important role of estuaries as nursery areas.
ERIC Educational Resources Information Center
Hoang, Giang T.; Kubo, Tomohiro; Young, Victor G., Jr.; Kautzky, Jacob A.; Wissinger, Jane E.
2015-01-01
Two introductory organic chemistry laboratory experiments are described based on the Diels-Alder reaction of 2,3,4,5-tetraphenylcyclopentadienone, which is synthesized prior to or in a one-pot reaction, with styrene. Students are presented with three possible products, the "endo" and "exo" diastereomers and the decarbonylated…
ERIC Educational Resources Information Center
Baar, Marsha R.; Falcone, Danielle; Gordon, Christopher
2010-01-01
Microwave heating enhanced the rate of three reactions typically performed in our undergraduate organic chemistry laboratory: a Diels-Alder cycloaddition, a Wittig salt formation, and a Williamson ether synthesis. Ninety-minute refluxes were shortened to 10 min using a laboratory-grade microwave oven. In addition, yields improved for the Wittig…
Retro iminonitroso Diels-Alder reactions: interconversion of nitroso cycloadducts
Yang, Baiyuan; Lin, Weimin; Krchnak, Viktor; Miller, Marvin J.
2009-01-01
Retro iminonitroso Diels-Alder reactions were investigated in both solution and solid phase. In thermal or Cu(I)-mediated reactions, interconversion of various nitroso cycloadducts occurred in the presence of separate dienes. Up to 99% of conversion was observed. Use of chiral ligands in the Cu(I)-medicated reactions gave new cycloadducts enantioselectively. PMID:20161032
A Computational Experiment of the Endo versus Exo Preference in a Diels-Alder Reaction
ERIC Educational Resources Information Center
Rowley, Christopher N.; Woo, Tom K.
2009-01-01
We have developed and tested a computational laboratory that investigates an endo versus exo Diels-Alder cycloaddition. This laboratory employed density functional theory (DFT) calculations to study the cycloaddition of N-phenylmaleimide to furan. The endo and exo stereoisomers of the product were distinguished by building the two isomers in a…
USDA-ARS?s Scientific Manuscript database
Bioassay-guided fractionation of a root extract of Sorocea muriculata led to the isolation and identification of two new oxygen heterocyclic Diels-Alder-type adducts, sorocenols G (1) and H (2), along with lupeol-3-(3'R-hydroxytetradecanoate) and oxyresveratrol. The structures of 1 and 2 were eluci...
Tests of a theory for diel activity and habitat selection
Steven F. Railsback; Bret C. Harvey; John W. Hayse; Kirk E. Lagory
2005-01-01
For many animals, selecting whether to forage during day or night is a critical fitness problem: at night, predation risks are lower but feeding is less efficient. Habitat selection is a closely related problem: the best location for nocturnal foraging could be too risky during daytime, and habitat that is safe and profitable in daytime may be unprofitable at night. We...
"In silico" mechanistic studies as predictive tools in microwave-assisted organic synthesis.
Rodriguez, A M; Prieto, P; de la Hoz, A; Díaz-Ortiz, A
2011-04-07
Computational calculations can be used as a predictive tool in Microwave-Assisted Organic Synthesis (MAOS). A DFT study on Intramolecular Diels-Alder reactions (IMDA) indicated that the activation energy of the reaction and the polarity of the stationary points are two fundamental parameters to determine "a priori" if a reaction can be improved by using microwave irradiation.
Benito-Lopez, Fernando; Verboom, Willem; Kakuta, Masaya; Gardeniers, J Han G E; Egberink, Richard J M; Oosterbroek, Edwin R; van den Berg, Albert; Reinhoudt, David N
2005-06-14
With a miniaturized (3 microL volume) fiber-optics based system for on-line measurement by UV/Vis spectroscopy, the reaction rate constants (at different pressures) and the activation volumes (deltaV(not =)) were determined for a nucleophilic aromatic substitution and an aza Diels-Alder reaction in a capillary microreactor.
The role of behavior in the dispersal of newly hatched gypsy moth larvae
Michael L. Mcmanus; Michael L. Mcmanus
1973-01-01
Newly hatched gypsy moth larvae are morphologically and behaviorally adapted for airborne dispersal. The diel periodicity of both hatching and dispersal from the egg mass and photopositive behavior assure that larvae are in optimal position for dispersal when air turbulence is maximal at midday. The rate of larval activity depends upon ambient temperature and relative...
Environmental Influences On Diel Calling Behavior In Baleen Whales
2015-09-30
and calm seas were infrequent and short (Figure 1b), making traditional shipboard marine mammal observations difficult. The real time detection...first use of real-time detection and reporting of marine mammal calls from autonomous underwater vehicles to adaptively plan research activities. 3...conferences: • 6th International Workshop on Detection, Classification, Localization, and Density Estimation (DCLDE) of Marine Mammals using
Effects of tide cycles on habitat selection and habitat partitioning by migrating shorebirds
Burger, J.; Howe, M.A.; Hahn, D.C.; Chase, J.
1977-01-01
We studied assemblages of feeding shorebirds in three intertidal habitats on the coast of New Jersey during August to document how species segregate spatially both among and within habitats and to determine the effects of tidal cycles on these patterns. The habitats were a sandy beach facing the ocean proper (outer beach), a sandy beach on the mainland side of a barrier island (inner beach), and a small mudflat adjacent to a Spartina alterniflora salt marsh. We were able to identify several microhabitats on the outer beach and mudflat. Most species fed in more than one habitat, but only two, Charadrius semipalmatus and Calidris canutus, used all three habitats regularly. Within habitats, most species exhibited strong preferences for the wettest areas, but we found differences among species in degrees of preference. The least amount of partitioning occurred on the inner beach, where birds crowded into a small zone near the water's edge and had frequent agonistic encounters suggesting intense competition. Shorebird feeding activity was partly a function of tide time: each habitat had a characteristic temporal pattern of use by shorebirds related to tide time rather than diel time; within habitats, we found species-characteristic feeding activity rhythms that were also a function of tide time. Feeding by most species peaked during the first 2 hours after low tide on the outer beach and mudflat. The results are discussed in terms of feeding strategies and interspecific competition.
Radioactive Phosphorylation of Alcohols to Monitor Biocatalytic Diels-Alder Reactions
Nierth, Alexander; Jäschke, Andres
2011-01-01
Nature has efficiently adopted phosphorylation for numerous biological key processes, spanning from cell signaling to energy storage and transmission. For the bioorganic chemist the number of possible ways to attach a single phosphate for radioactive labeling is surprisingly small. Here we describe a very simple and fast one-pot synthesis to phosphorylate an alcohol with phosphoric acid using trichloroacetonitrile as activating agent. Using this procedure, we efficiently attached the radioactive phosphorus isotope 32P to an anthracene diene, which is a substrate for the Diels-Alderase ribozyme—an RNA sequence that catalyzes the eponymous reaction. We used the 32P-substrate for the measurement of RNA-catalyzed reaction kinetics of several dye-labeled ribozyme variants for which precise optical activity determination (UV/vis, fluorescence) failed due to interference of the attached dyes. The reaction kinetics were analyzed by thin-layer chromatographic separation of the 32P-labeled reaction components and densitometric analysis of the substrate and product radioactivities, thereby allowing iterative optimization of the dye positions for future single-molecule studies. The phosphorylation strategy with trichloroacetonitrile may be applicable for labeling numerous other compounds that contain alcoholic hydroxyl groups. PMID:21731729
NASA Astrophysics Data System (ADS)
Rosenblatt, Adam E.; Heithaus, Michael R.; Mazzotti, Frank J.; Cherkiss, Michael; Jeffery, Brian M.
2013-12-01
Movement and habitat use patterns are fundamental components of the behaviors of mobile animals and help determine the scale and types of interactions they have with their environments. These behaviors are especially important to quantify for top predators because they can have strong effects on lower trophic levels as well as the wider ecosystem. Many studies of top predator movement and habitat use focus on general population level trends, which may overlook important intra-population variation in behaviors that now appear to be common. In an effort to better understand the prevalence of intra-population variation in top predator movement behaviors and the potential effects of such variation on ecosystem dynamics, we examined the movement and habitat use patterns of a population of adult American alligators (Alligator mississippiensis) in a subtropical estuary for nearly four years. We found that alligators exhibited divergent behaviors with respect to activity ranges, movement rates, and habitat use, and that individualized behaviors were stable over multiple years. We also found that the variations across the three behavioral metrics were correlated such that consistent behavioral types emerged, specifically more exploratory individuals and more sedentary individuals. Our study demonstrates that top predator populations can be characterized by high degrees of intra-population variation in terms of movement and habitat use behaviors that could lead to individuals filling different ecological roles in the same ecosystem. By extension, one-size-fits-all ecosystem and species-specific conservation and management strategies that do not account for potential intra-population variation in top predator behaviors may not produce the desired outcomes in all cases.
Rosenblatt, Adam E.; Heithaus, Michael R.; Mazzotti, Frank M; Cherkiss, Michael S.; Jeffery, Brian M.
2013-01-01
Movement and habitat use patterns are fundamental components of the behaviors of mobile animals and help determine the scale and types of interactions they have with their environments. These behaviors are especially important to quantify for top predators because they can have strong effects on lower trophic levels as well as the wider ecosystem. Many studies of top predator movement and habitat use focus on general population level trends, which may overlook important intra-population variation in behaviors that now appear to be common. In an effort to better understand the prevalence of intrapopulation variation in top predator movement behaviors and the potential effects of such variation on ecosystem dynamics, we examined the movement and habitat use patterns of a population of adult American alligators (Alligator mississippiensis) in a subtropical estuary for nearly four years. We found that alligators exhibited divergent behaviors with respect to activity ranges, movement rates, and habitat use, and that individualized behaviors were stable over multiple years. We also found that the variations across the three behavioral metrics were correlated such that consistent behavioral types emerged, specifically more exploratory individuals and more sedentary individuals. Our study demonstrates that top predator populations can be characterized by high degrees of intra-population variation in terms of movement and habitat use behaviors that could lead to individuals filling different ecological roles in the same ecosystem. By extension, one-size-fits-all ecosystem and species-specific conservation and management strategies that do not account for potential intra-population variation in top predator behaviors may not produce the desired outcomes in all cases.
NASA Astrophysics Data System (ADS)
Chamberlain, Samuel D.; Verfaillie, Joseph; Eichelmann, Elke; Hemes, Kyle S.; Baldocchi, Dennis D.
2017-11-01
Corrections accounting for air density fluctuations due to heat and water vapour fluxes must be applied to the measurement of eddy-covariance fluxes when using open-path sensors. Experimental tests and ecosystem observations have demonstrated the important role density corrections play in accurately quantifying carbon dioxide (CO2) fluxes, but less attention has been paid to evaluating these corrections for methane (CH4) fluxes. We measured CH4 fluxes with open-path sensors over a suite of sites with contrasting CH4 emissions and energy partitioning, including a pavement airfield, two negligible-flux ecosystems (drained alfalfa and pasture), and two high-flux ecosystems (flooded wetland and rice). We found that density corrections successfully re-zeroed fluxes in negligible-flux sites; however, slight overcorrection was observed above pavement. The primary impact of density corrections varied over negligible- and high-flux ecosystems. For negligible-flux sites, corrections led to greater than 100% adjustment in daily budgets, while these adjustments were only 3-10% in high-flux ecosystems. The primary impact to high-flux ecosystems was a change in flux diel patterns, which may affect the evaluation of relationships between biophysical drivers and fluxes if correction bias exists. Additionally, accounting for density effects to high-frequency CH4 fluctuations led to large differences in observed CH4 flux cospectra above negligible-flux sites, demonstrating that similar adjustments should be made before interpreting CH4 cospectra for comparable ecosystems. These results give us confidence in CH4 fluxes measured by open-path sensors, and demonstrate that density corrections play an important role in adjusting flux budgets and diel patterns across a range of ecosystems.
Sbragaglia, Valerio; Lamanna, Francesco; M. Mat, Audrey; Rotllant, Guiomar; Joly, Silvia; Ketmaier, Valerio; de la Iglesia, Horacio O.; Aguzzi, Jacopo
2015-01-01
The Norway lobster, Nephrops norvegicus, is a burrowing decapod with a rhythmic burrow emergence (24 h) governed by the circadian system. It is an important resource for European fisheries and its behavior deeply affects its availability. The current knowledge of Nephrops circadian biology is phenomenological as it is currently the case for almost all crustaceans. In attempt to elucidate the putative molecular mechanisms underlying circadian gene regulation in Nephrops, we used a transcriptomics approach on cDNA extracted from the eyestalk, a structure playing a crucial role in controlling behavior of decapods. We studied 14 male lobsters under 12–12 light-darkness blue light cycle. We used the Hiseq 2000 Illumina platform to sequence two eyestalk libraries (under light and darkness conditions) obtaining about 90 millions 100-bp paired-end reads. Trinity was used for the de novo reconstruction of transcriptomes; the size at which half of all assembled bases reside in contigs (N50) was equal to 1796 (light) and 2055 (darkness). We found a list of candidate clock genes and focused our attention on canonical ones: timeless, period, clock and bmal1. The cloning of assembled fragments validated Trinity outputs. The putative Nephrops clock genes showed high levels of identity (blastx on NCBI) with known crustacean clock gene homologs such as Eurydice pulchra (period: 47%, timeless: 59%, bmal1: 79%) and Macrobrachium rosenbergii (clock: 100%). We also found a vertebrate-like cryptochrome 2. RT-qPCR showed that only timeless had a robust diel pattern of expression. Our data are in accordance with the current knowledge of the crustacean circadian clock, reinforcing the idea that the molecular clockwork of this group shows some differences with the established model in Drosophila melanogaster. PMID:26524198
Mella-Flores, Daniella; Six, Christophe; Ratin, Morgane; Partensky, Frédéric; Boutte, Christophe; Le Corguillé, Gildas; Marie, Dominique; Blot, Nicolas; Gourvil, Priscillia; Kolowrat, Christian; Garczarek, Laurence
2012-01-01
Prochlorococcus and Synechococcus, which numerically dominate vast oceanic areas, are the two most abundant oxygenic phototrophs on Earth. Although they require solar energy for photosynthesis, excess light and associated high UV radiations can induce high levels of oxidative stress that may have deleterious effects on their growth and productivity. Here, we compared the photophysiologies of the model strains Prochlorococcus marinus PCC 9511 and Synechococcus sp. WH7803 grown under a bell-shaped light/dark cycle of high visible light supplemented or not with UV. Prochlorococcus exhibited a higher sensitivity to photoinactivation than Synechococcus under both conditions, as shown by a larger drop of photosystem II (PSII) quantum yield at noon and different diel patterns of the D1 protein pool. In the presence of UV, the PSII repair rate was significantly depressed at noon in Prochlorococcus compared to Synechococcus. Additionally, Prochlorococcus was more sensitive than Synechococcus to oxidative stress, as shown by the different degrees of PSII photoinactivation after addition of hydrogen peroxide. A transcriptional analysis also revealed dramatic discrepancies between the two organisms in the diel expression patterns of several genes involved notably in the biosynthesis and/or repair of photosystems, light-harvesting complexes, CO2 fixation as well as protection mechanisms against light, UV, and oxidative stress, which likely translate profound differences in their light-controlled regulation. Altogether our results suggest that while Synechococcus has developed efficient ways to cope with light and UV stress, Prochlorococcus cells seemingly survive stressful hours of the day by launching a minimal set of protection mechanisms and by temporarily bringing down several key metabolic processes. This study provides unprecedented insights into understanding the distinct depth distributions and dynamics of these two picocyanobacteria in the field. PMID:23024637
Simulation of Lake Victoria Circulation Patterns Using the Regional Ocean Modeling System (ROMS).
Nyamweya, Chrispine; Desjardins, Christopher; Sigurdsson, Sven; Tomasson, Tumi; Taabu-Munyaho, Anthony; Sitoki, Lewis; Stefansson, Gunnar
2016-01-01
Lake Victoria provides important ecosystem services including transport, water for domestic and industrial uses and fisheries to about 33 million inhabitants in three East African countries. The lake plays an important role in modulating regional climate. Its thermodynamics and hydrodynamics are also influenced by prevailing climatic and weather conditions on diel, seasonal and annual scales. However, information on water temperature and circulation in the lake is limited in space and time. We use a Regional Oceanographic Model System (ROMS) to simulate these processes from 1st January 2000 to 31st December 2014. The model is based on real bathymetry, river runoff and atmospheric forcing data using the bulk flux algorithm. Simulations show that the water column exhibits annual cycles of thermo-stratification (September-May) and mixing (June-August). Surface water currents take different patterns ranging from a lake-wide northward flow to gyres that vary in size and number. An under flow exists that leads to the formation of upwelling and downwelling regions. Current velocities are highest at the center of the lake and on the western inshore waters indicating enhanced water circulation in those areas. However, there is little exchange of water between the major gulfs (especially Nyanza) and the open lake, a factor that could be responsible for the different water quality reported in those regions. Findings of the present study enhance understanding of the physical processes (temperature and currents) that have an effect on diel, seasonal, and annual variations in stratification, vertical mixing, inshore-offshore exchanges and fluxes of nutrients that ultimately influence the biotic distribution and trophic structure. For instance information on areas/timing of upwelling and vertical mixing obtained from this study will help predict locations/seasons of high primary production and ultimately fisheries productivity in Lake Victoria.
Mella-Flores, Daniella; Six, Christophe; Ratin, Morgane; Partensky, Frédéric; Boutte, Christophe; Le Corguillé, Gildas; Marie, Dominique; Blot, Nicolas; Gourvil, Priscillia; Kolowrat, Christian; Garczarek, Laurence
2012-01-01
Prochlorococcus and Synechococcus, which numerically dominate vast oceanic areas, are the two most abundant oxygenic phototrophs on Earth. Although they require solar energy for photosynthesis, excess light and associated high UV radiations can induce high levels of oxidative stress that may have deleterious effects on their growth and productivity. Here, we compared the photophysiologies of the model strains Prochlorococcus marinus PCC 9511 and Synechococcus sp. WH7803 grown under a bell-shaped light/dark cycle of high visible light supplemented or not with UV. Prochlorococcus exhibited a higher sensitivity to photoinactivation than Synechococcus under both conditions, as shown by a larger drop of photosystem II (PSII) quantum yield at noon and different diel patterns of the D1 protein pool. In the presence of UV, the PSII repair rate was significantly depressed at noon in Prochlorococcus compared to Synechococcus. Additionally, Prochlorococcus was more sensitive than Synechococcus to oxidative stress, as shown by the different degrees of PSII photoinactivation after addition of hydrogen peroxide. A transcriptional analysis also revealed dramatic discrepancies between the two organisms in the diel expression patterns of several genes involved notably in the biosynthesis and/or repair of photosystems, light-harvesting complexes, CO(2) fixation as well as protection mechanisms against light, UV, and oxidative stress, which likely translate profound differences in their light-controlled regulation. Altogether our results suggest that while Synechococcus has developed efficient ways to cope with light and UV stress, Prochlorococcus cells seemingly survive stressful hours of the day by launching a minimal set of protection mechanisms and by temporarily bringing down several key metabolic processes. This study provides unprecedented insights into understanding the distinct depth distributions and dynamics of these two picocyanobacteria in the field.
Smith, Richard L.; Repert, Deborah A.; Hart, Charles P.
2009-01-01
Water originating from coal-bed natural gas (CBNG) production wells typically contains ammonium and is often disposed via discharge to ephemeral channels. A study conducted in the Powder River Basin, Wyoming, documented downstream changes in CBNG water composition, emphasizing nitrogen-cycling processes and the fate of ammonium. Dissolved ammonium concentrations from 19 CBNG discharge points ranged from 95 to 527 μM. Within specific channels, ammonium concentrations decreased with transport distance, with subsequent increases in nitrite and nitrate concentrations. Removal efficiency, or uptake, of total dissolved inorganic nitrogen (DIN) varied between channel types. DIN uptake was greater in the gentle-sloped, vegetated channel as compared to the incised, steep, and sparsely vegetated channel and was highly correlated with diel patterns of incident light and dissolved oxygen concentration. In a larger main channel with multiple discharge inputs (n = 13), DIN concentrations were >300 μM, with pH > 8.5, after 5 km of transport. Ammonium represented 25−30% of the large-channel DIN, and ammonium concentrations remained relatively constant with time, with only a weak diel pattern evident. In July 2003, the average daily large-channel DIN load was 23 kg N day−1entering the Powder River, an amount which substantially increased the total Powder River DIN load after the channel confluence. These results suggest that CBNG discharge may be an important source of DIN to western watersheds, at least at certain times of the year, and that net oxidation and/or removal is dependent upon the extent of contact with sediment and biomass, type of drainage channel, and time of day.
Foster, Robert W; Benhamou, Laure; Porter, Michael J; Bučar, Dejan-Krešimir; Hailes, Helen C; Tame, Christopher J; Sheppard, Tom D
2015-04-13
The [4+2] cycloaddition of 3-alkoxyfurans with N-substituted maleimides provides the first general route for preparing endo-cantharimides. Unlike the corresponding reaction with 3H furans, the reaction can tolerate a broad range of 2-substitued furans including alkyl, aromatic, and heteroaromatic groups. The cycloaddition products were converted into a range of cantharimide products with promising lead-like properties for medicinal chemistry programs. Furthermore, the electron-rich furans are shown to react with a variety of alternative dienophiles to generate 7-oxabicyclo[2.2.1]heptane derivatives under mild conditions. DFT calculations have been performed to rationalize the activation effect of the 3-alkoxy group on a furan Diels-Alder reaction. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
NASA Astrophysics Data System (ADS)
Rueda, Jose L.; Urra, Javier; Salas, Carmen
2008-09-01
The diel and seasonal variation of molluscs living in a Zostera marina bed (12-14 m depth) from southern Spain have been studied for one year using a small Agassiz trawl for collecting the samples (222 m2). The frequent and dominant species were very similar in both diurnal and nocturnal samples, including mainly gastropods such as Jujubinus striatus, Nassarius pygmaeus, Mitrella minor, Calliostoma planatum, Rissoa membranacea or Smaragdia viridis. Nevertheless, a significant increase of abundance of scavengers (e.g. Nassarius spp.) and carnivores (e.g. cephalopods) was registered in nocturnal samples. The abundance was maximal in spring and summer in diurnal and nocturnal samples and also in autumn for nocturnal ones, displaying significantly higher values in nocturnal samples. The species richness, diversity and evenness displayed a similar seasonal trend for diurnal and nocturnal samples, with maximum values during summer months. Monthly variation of the molluscan composition (species presence-absence data) was more acute than diel variation, according to the Cluster, MDS and ANOSIM results. Nevertheless, both monthly and diel changes in the structure (species abundance data) of the molluscan taxocoenosis were important throughout the year. Diel changes in the structure of the molluscan fauna are related to an increase of abundance of some species at nighttime due to vertical movements from the sediment to the shoots or along them (e.g. J. striatus, Nassarius spp.) or due to horizontal movements from adjacent habitats (e.g. cephalopods). Nevertheless, some species such as Rissoa spp. or Bittium spp. stay on the leaves of Z. marina during day as well as nighttime.
Diel rhythms in the volatile emission of apple and grape foliage.
Giacomuzzi, Valentino; Cappellin, Luca; Nones, Stefano; Khomenko, Iuliia; Biasioli, Franco; Knight, Alan L; Angeli, Sergio
2017-06-01
This study investigated the diel emission of volatile organic compounds (VOCs) from intact apple (Malus x domestica Borkh., cv. Golden Delicious) and grape (Vitis vinifera L., cv. Pinot Noir) foliage. Volatiles were monitored continuously for 48 h by proton transfer reaction - time of flight - mass spectrometry (PTR-ToF-MS). In addition, volatiles were collected by closed-loop-stripping-analysis (CLSA) and characterized by gas chromatography-mass spectrometry (GC-MS) after 1 h and again 24 and 48 h later. Fourteen and ten volatiles were characterized by GC-MS in apple and grape, respectively. The majority of these were terpenes, followed by green leaf volatiles, and aromatic compounds. The PTR-ToF-MS identified 10 additional compounds and established their diel emission rhythms. The most abundant volatiles displaying a diel rhythm included methanol and dimethyl sulfide in both plants, acetone in grape, and mono-, homo- and sesquiterpenes in apple. The majority of volatiles were released from both plants during the photophase; whereas methanol, CO 2 , methyl-butenol and benzeneacetaldehyde were released at significantly higher levels during the scotophase. Acetaldehyde, ethanol, and some green leaf volatiles showed distinct emission bursts in both plants following the daily light switch-off. These new results obtained with a combined analytical approach broaden our understanding of the rhythms of constitutive volatile release from two important horticultural crops. In particular, diel emission of sulfur and nitrogen-containing volatiles are reported here for the first time in these two crops. Copyright © 2017. Published by Elsevier Ltd.
Diel rhythmicity of lipid-body formation in a coral- Symbiodinium endosymbiosis
NASA Astrophysics Data System (ADS)
Chen, W.-N. U.; Kang, H.-J.; Weis, V. M.; Mayfield, A. B.; Jiang, P.-L.; Fang, L.-S.; Chen, C.-S.
2012-06-01
The biogenesis of intracellular lipid bodies (LBs) is dependent upon the symbiotic status between host corals and their intracellular dinoflagellates (genus Symbiodinium), though aside from this observation, little is known about LB behavior and function in this globally important endosymbiosis. The present research aimed to understand how LB formation and density are regulated in the gastrodermal tissue layer of the reef-building coral Euphyllia glabrescens. After tissue fixation and labeling with osmium tetroxide, LB distribution and density were quantified by imaging analysis of serial cryo-sections, and a diel rhythmicity was observed; the onset of solar irradiation at sunrise initiated an increase in LB density and size, which peaked at sunset. Both LB density and size then decreased to basal levels at night. On a seasonal timescale, LB density was found to be significantly positively correlated with seasonal irradiation, with highest densities found in the summer and lowest in the fall. In terms of LB lipid composition, only the concentration of wax esters, and not triglycerides or sterols, exhibited diel variability. This suggests that the metabolism and accumulation of lipids in LBs is at least partially light dependent. Ultrastructural examinations revealed that the LB wax ester concentration correlated with the number of electron-transparent inclusion bodies. Finally, there was a directional redistribution of the LB population across the gastroderm over the diel cycle. Collectively, these data reveal that coral gastrodermal LBs vary in composition and intracellular location over diel cycles, features which may shed light on their function within this coral-dinoflagellate mutualism.
Parker, Stephen R.; Poulson, Simon R.; Gammons, Christopher H.; DeGrandpre, Michael D.
2005-01-01
Rivers with high biological productivity typically show substantial increases in pH and dissolved oxygen (DO) concentration during the day and decreases at night, in response to changes in the relative rates of aquatic photosynthesis and respiration. These changes, coupled with temperature variations, may impart diel (24-h) fluctuations in the concentration of trace metals, nutrients, and other chemical species. A better understanding of diel processes in rivers is needed and will lead to improved methods of data collection for both monitoring and research purposes. Previous studies have used stable isotopes of dissolved oxygen (DO) and dissolved inorganic carbon (DIC) as tracers of geochemical and biological processes in streams, lakes, and marine systems. Although seasonal variation in δ18O of DO in rivers and lakes has been documented, no study has investigated diel changes in this parameter. Here, we demonstrate large (up to 13‰) cycles in δ18O-DO for two late summer sampling periods in the Big Hole River of southwest Montana and illustrate that these changes are correlated to variations in the DO concentration, the C-isotopic composition of DIC, and the primary productivity of the system. The magnitude of the diel cycle in δ18O-DO was greater in August versus September because of the longer photoperiod and warmer water temperatures. This study provides another biogeochemical tool for investigating the O2 and C budgets in rivers and may also be applicable to lake and groundwater systems.
C.B. Graham; H.R. Barnard; K.L. Kavanagh; J.P. McNamara
2012-01-01
Diel fluctuations can comprise a significant portion of summer discharge in small to medium catchments. The source of these signals and the manner in which they are propagated to stream gauging sites is poorly understood. In this work, we analysed stream discharge from 15 subcatchments in Dry Creek, Idaho, Reynolds Creek, Idaho, and HJ Andrews, Oregon. We identified...
Madeleine Eckmann; Jason Dunham; Edward J. Connor; Carmen A. Welch
2016-01-01
Many species living in deeper lentic ecosystems exhibit daily movements that cycle through the water column, generally referred to as diel vertical migration (DVM). In this study, we applied bioenergetics modelling to evaluate growth as a hypothesis to explain DVM by bull trout (Salvelinus confluentus) in a thermally stratified reservoir (Ross Lake...
Diterpenoid alkaloids from the roots of Aconitum brachypodum Diels.
Yang, Li-Guo; Zhang, Ying-Jie; Xie, Jia-Ying; Xia, Wei-Jun; Zhang, Hai-Yuan; Tang, Meng-Yun; Mei, Shuang-Xi; Cui, Tao; Wang, Jing-Kun; Zhu, Zhao-Yun
2016-09-01
A new diterpenoid alkaloid, named bullatine H (1), along with 10 known diterpenoid alkaloids were isolated from the roots of Aconitum brachypodum Diels (Ranunculaceae). The structure of 1 was elucidated by analysis of its spectroscopic data. It should be noted that compound 1 is the first example with 11, 13-dioxygenated denudatine-type diterpenoid alkaloid isolated from Aconitum brachypodum.
ERIC Educational Resources Information Center
Sauvage, Xavier; Delaude, Lionel
2008-01-01
The synthesis of "N"-benzyl-2-azanorbornene via aqueous hetero Diels-Alder reaction of cyclopentadiene and benzyliminium chloride formed in situ from benzylamine hydrochloride and formaldehyde is described. Characterization of the product was achieved by IR and NMR spectroscopies. The spectral data acquired are thoroughly discussed. Numerous…
Li, Weinan; Kong, Yanjun; Cong, Xiangyu
2016-01-01
Using multi-fractal detrended fluctuation analysis (MF-DFA), the scaling features of wind speed time series (WSTS) could be explored. In this paper, we discuss the influence of sub-daily variation, which is a natural feature of wind, in MF-DFA of WSTS. First, the choice of the lower bound of the segment length, a significant parameter of MF-DFA, was studied. The results of expanding the lower bound into sub-daily scope shows that an abrupt declination and discrepancy of scaling exponents is caused by the inability to keep the whole diel process of wind in one single segment. Additionally, the specific value, which is effected by the sub-daily feature of local meteo-climatic, might be different. Second, the intra-day temporal order of wind was shuffled to determine the impact of diel variation on scaling exponents of MF-DFA. The results illustrate that disregarding diel variation leads to errors in scaling. We propose that during the MF-DFA of WSTS, the segment length should be longer than 1 day and the diel variation of wind should be maintained to avoid abnormal phenomena and discrepancy in scaling exponents. PMID:26741491
Design and Synthesis of a Library of Tetracyclic Hydroazulenoisoindoles
Brummond, Kay M.; Mao, Shuli; Shinde, Sunita N.; Johnston, Paul J.; Day, Billy W.
2009-01-01
Forty-four tetracyclic hydroazulenoisoindoles were synthesized via a tandem cyclopropanation/Cope rearrangement followed by a Diels-Alder sequence from easily available five-membered cyclic cross-conjugated trienones. These trienones were obtained from two different routes depending upon whether R1 and R2 are alkyl or amino acid derived functional groups, via a rhodium(I)-catalyzed cycloisomerization reaction. In order to increase diversity, four maleimides and two 1,2,4-triazoline-3,5-diones were used as dienophiles in the Diels-Alder step. Several Diels-Alder adducts were further reacted under palladium-catalyzed hydrogenation conditions, leading to a diastereoselective reduction of the trisubstituted double bond. This library has demonstrated rapid access to a variety of structurally complex natural product-like compounds via stereochemical diversity and building block diversity approaches. PMID:19366169
Methane fluxes from the mound-building termite species of North Australian savannas
NASA Astrophysics Data System (ADS)
Jamali, H.; Livesely, S. J.; Arndt, S. K.; Dawes-Gromadzki, T.; Cook, G. D.; Hutley, L.
2009-04-01
Termites are estimated to contribute 3-19% to the global methane emissions. These estimates have large uncertainties because of the limited number of field-based studies and species studied, as well as issues of diel and seasonal variation. We measured methane fluxes from four common mound-building termite species (Microcerotermes nervosus, n=26; M. serratus, n=4; Tumulitermes pastinator, n=5; and Amitermes darwini, n=4) in tropical savannas near Darwin in the Northern Territory, Australia. Methane fluxes from replicated termite mounds were measured in the field using manual chambers with fluxes reported on a mound volume basis. Methane flux was measured in both wet and dry seasons and diel variation was investigated by measuring methane flux every 4 hours over a 24 hour period. Mound temperature was measured concurrently with flux to examine this relationship. In addition, five M. nervosus mounds removed from the field and incubated under controlled temperature conditions over a 24 hour period to remove the effect of varying temperature. During the observation campaigns, mean monthly minimum and maximum temperatures for February (wet season) were 24.7 and 30.8°C, respectively, and were 20.1 to 31.4 °C in June (dry season). Annual rainfall in 2008 for Darwin was 1970.1 mm, with a maximum of 670 mm falling in February and no rain in May and June. Methane fluxes were greatest in the wet season for all species, ranging from 265.1±101.1 (T. pastinator) to 2256.6±757.1 (M. serratus) µg CH4-C/m3/h. In the dry season, methane fluxes were at their lowest, ranging from 10.0±5.5 (T. pastinator) to 338.0±165.9 (M. serratus) µg CH4-C/m3/h. On a diel basis, methane fluxes were smallest at the coolest time of the day (~0700 hrs) and greatest at the warmest (~1400 hrs) for all species, and for both wet and dry seasons. Typical diel variation in flux from M. serratus dominated mounds ranged from 902.6±261.9 to 1392.1±408.1 µg CH4-C/m3/h in wet season and 99.6±57.4 to 556.2±254.9 µg CH4-C/m3/h in dry season. While mounds of M. nervosus had diel variations in methane fluxes in the field, no diel variation was observed when incubated under constant laboratory temperature for 24 hours. This demonstrates that diel variation was not due to the movement of termites in and out of the mounds, but was due to temperature variation. Methane flux varied significantly according to termite species and at seasonal and diel time scales which, if not accounted for, could result in large under- or over-estimation of methane emissions from termites when flux data are extrapolated to landscape scales.
Spatial and Temporal Patterns In Ecohydrological Separation
NASA Astrophysics Data System (ADS)
Jarvis, S. K.; Barnard, H. R.; Singha, K.; Harmon, R. E.; Szutu, D.
2017-12-01
The model of ecohydrological separation suggests that trees source water from a different subsurface pool than what is contributing to stream flow during dry periods, however diel fluctuations in stream flow and transpiration are tightly coupled. To better understand the mechanism of this coupling, this study examines spatiotemporal patterns in water isotopic relationships between tree, soil, and stream water. Preliminary analysis of data collected in 2015 show a trend in δ18O enrichment in xylem water, suggesting an increased reliance on enriched soil water not flowing to the stream as the growing season progresses, while xylem samples from 2016, a particularly wet year, do not have this trend. Variations in these temporal trends are explored with regard to distance from stream, aspect of hillslope, position in the watershed, size of the tree, and soil depth. Additionally, a near-stream site is examined at high resolution using water isotope data, sap flow, and electrical resistivity surveying to examine soil moisture and water use patterns across the riparian-hillslope transition.
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 behavior. Beyond situations of contest competition, rank status appears to influence the extent to which individuals can modify their movement strategies across periods with differing forage availability. Large-scale spatiotemporal resource complexity not only impacts fine scale movement and optimal foraging strategies directly, but likely impacts rates of inter- and intra-specific interactions and competition resulting in socially based movement responses to ecological dynamics.
Fabian G. Scholz; Sandra J. Bucci; Guillermo Goldstein; Frederick C. Meinzer; Agusto C. Franco; Fernando Miralles-Wilhelm
2008-01-01
Relationships between diel changes in stem expansion and contraction and discharge and refilling of stem water storage tissues were studied in six dominant Neotropical savanna (cerrado) tree species from central Brazil. Two stem tissues were studied, the active xylem or sapwood and the living tissues located between the cambium and the cork, made up predominantly of...
Pulsed remineralisation in the northwestern Mediterranean Sea: a hypothesis
NASA Astrophysics Data System (ADS)
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 activity of the nonmigrating midwater populations. Our results confirm the recent finding that the particulate compartment is not the major source of the observed instantaneous remineralisation rate and shed a new light on the fate of organic matter in the aphotic zone.
NASA Astrophysics Data System (ADS)
Aguzzi, J.; Sanchez-Pardo, J.; García, J. A.; Sardà, F.
2009-10-01
Few studies have been conducted to quantify and understand the role of melatonin in invertebrates, and particularly in crustaceans and in deep-sea animals. In this study, we examined day-night differences in haemolymph melatonin of the burrowing decapod crustacean Nephrops norvegicus (L.) during exposure to cycles of monochromatic blue light (480 nm) and darkness cycles of 10 and 0.1 lx. These differential intensity conditions simulate illumination at the depth of the shelf (80-100 m) and of the slope (300-400 m), where these lobster populations are chiefly found in the Western Mediterranean Sea. Our objectives were: (a) to verify the presence of melatonin in the haemolymph of this species using liquid chromatography/tandem mass spectrometry (LC-MS/MS) and fluorescence HPLC (HPLC); and (b) to study the relationship between diel variations in melatonin concentration and locomotor rhythms, in order to examine whether the former influences behaviour. Melatonin was identified in LC-MS/MS by Q1 and Q3 mass peaks at an elution time of 3.7 min, and it was also detected by HPLC. Melatonin concentration was found to be two orders of magnitude higher at 10 lx (4.8±5.3 ng ml -1) than at 0.1 lx (0.06±0.03 ng ml -1). Also, the increase at daytime in 10 lx was absent in 0.1 lx. When the locomotor rhythm of animals exposed to both photoperiod regimes was compared, the diel periodicity was found to be preserved, but the timing of activity shifted from night to day. Extrapolating these data to the field, we interpret our results to mean that locomotor activity preserves its diel character, but not its phase and amplitude, in a bathymetric range where haemolymph melatonin reduces its concentration and rhythmic fluctuation.
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 dispersal of colonies throughout the water column when the water column mixed more easily. RB was used to estimate suspended solids concentrations (SSC). Correlations of depth-integrated SSC with currents or air temperatures suggest that depth-integrated water column mass decreased under conditions of greater water column stability and weaker currents. Results suggest that the use of measured vertical velocity and acoustic backscatter as a surrogate for suspended material has the potential to contribute significant additional insight into dynamics of Aphanizomenon flos-aquae colonies in Upper Klamath Lake, south-central Oregon.
NASA Astrophysics Data System (ADS)
Dean, Cayla; Soloviev, Alexander; Hirons, Amy; Frank, Tamara; Wood, Jon
2015-04-01
Recent studies suggest that diel vertical migrations of zooplankton may have an impact on ocean mixing, though details are not completely clear. A strong sound scattering layer of zooplankton undergoing diel vertical migrations was observed in Saanich Inlet, British Colombia, Canada by Kunze et al. (2006). In this study, a shipboard 200-kHz echosounder was used to track vertical motion of the sound scattering layer, and microstructure profiles were collected to observe turbulence. An increase of dissipation rate of turbulent kinetic energy by four to five orders of magnitude was measured during diel vertical migrations of zooplankton in one case (but not observed during other cases). A strong sound scattering layer undergoing diel vertical migration was also observed in the Straits of Florida via a bottom mounted acoustic Doppler current profiler at 244 m isobath. A 3-D non-hydrostatic computational fluid dynamics model with Lagrangian particle injections (a proxy for migrating zooplankton) via a discrete phase model was used to simulate the effect of diel vertical migrations on the turbulence for both Saanich Inlet and the Straits of Florida. The model was initialized with idealized (but based on observation) density and velocity profiles. Particles, with buoyancy adjusted to serve as a proxy for vertically swimming zooplankton, were injected to simulate diel vertical migration cycles. Results of models run with extreme concentrations of particles showed an increase in dissipation rate of turbulent kinetic energy of approximately five orders of magnitude over background turbulence during migration of particles in both Saanich Inlet and the Straits of Florida cases (though direct relation of the turbulence produced by buoyant particles and swimming organisms isn't straightforward). This increase was quantitatively consistent, with turbulence measurements by Kunze et al. (2006). When 10 times fewer particles were injected into the model, the effect on dissipation rate of turbulent kinetic energy was an order of magnitude smaller than that from the extreme concentration. At a concentration of particles 100 times smaller than the extreme concentration, there was no longer an observable effect. In the Straits of Florida, direct turbulence measurements were not available to make a quantitative comparison. However, a small, but statistically significant decrease in northward current velocity profiles during migration times were observed after averaging these profiles over 11 months. A small decrease of current velocity connected to the vertical migrations of particles was reproduced in the Straits of Florida model case. The deviations in the velocity profiles can be explained by the increase in turbulent mixing during vertical migration periods.
Michael J. Jakober; Thomas E. McMahon; Russell F. Thurow
2000-01-01
We used underwater observation to determine diel habitat partitioning between bull charr, Salvelinus confluentus, and cutthroat trout, Oncorhynchus clarki, during fall and winter (0.1-8.3°C) in two Rocky Mountain streams that differed in habitat availability. The majority (>70%) of both species emerged from concealment cover at night, though bull charr exhibited a...
Fourfold Diels-Alder reaction of tetraethynylsilane.
Geyer, Florian L; Rode, Alexander; Bunz, Uwe H F
2014-12-08
A series of ethynylated silanes, including tetraethynylsilane, was treated with tetraphenylcyclopentadienone at 300 °C under microwave irradiation to give the aromatized Diels-Alder adducts as sterically encumbered mini-dendrimers with up to 20 benzene rings. The sterically most congested adducts display red-shifted emission through intramolecular π-π interactions in the excited state. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Shore, Gjergji; Organ, Michael G
2008-02-21
Thin Pd films have been deposited on the inside of capillary-sized tubes through which compounds undergoing Diels-Alder reactions have been flowed while being heated with microwave irradiation; dramatic rate accelerations are observed in the presence of the film, which has been shown to play both a heating and catalytic role.
Indole synthesis by palladium-catalyzed tandem allylic isomerization - furan Diels-Alder reaction.
Xu, Jie; Wipf, Peter
2017-08-30
A Pd(0)-catalyzed elimination of an allylic acetate generates a π-allyl complex that is postulated to initiate a novel intramolecular Diels-Alder cycloaddition to a tethered furan (IMDAF). Under the reaction conditions, this convergent, microwave-accelerated cascade process provides substituted indoles in moderate to good yields after Pd-hydride elimination, aromatization by dehydration, and in situ N-Boc cleavage.
Diels-Alder Synthesis of endo-cis-N-phenylbicyclo[2.2.2]oct-5-en-2,3-dicarboximide
ERIC Educational Resources Information Center
Baar, Marsha R.; Wustholz, Kristin
2005-01-01
A study investigated the Diels-Alder synthesis of endo-cis-N-phenylbicyclo [2.2.2]oct-5-en-2,3-dicarboximide. The amount of time taken by a reaction between the 1,3-cyclohexadiene and N-phenylmaleimide at room temperature and also whether the desired cycloadduct would precipitate directly from the reaction mixture was examined.
Origins of Stereoselectivity in Diels-Alder Cycloadditions Catalyzed by Chiral Imidazolidinones
Gordillo, Ruth; Houk, K. N.
2011-01-01
B3LYP/6-31G(d) density functional theory has been used to study Diels-Alder reactions of cyclopentadiene with α,β-unsaturated aldehydes and ketones organocatalyzed by MacMillan’s chiral imidazolidinones. Preferred conformations of transition structures and reaction intermediates have been located. The dramatically different reactivities and enantioselectivities exhibited by two similar chiral imidazolidinones are rationalized. PMID:16536527
Nimmo, Chelsea M; Shoichet, Molly S
2011-11-16
The click chemistry era has generated a library of versatile "spring-loaded" reactions that offer high yields, regio- and stereospecificity, and outstanding functional group tolerance. These powerful transformations are particularly advantageous for the design of sophisticated biomaterials that require high levels of precision and control, namely, materials that promote tissue regeneration such as hydrogels, 2D functionalized substrates, and 3D biomimetic scaffolds. In this review, the synthesis and application of regenerative biomaterials via click chemistry are summarized. Particular emphasis is placed on the copper(I)-catalyzed alkyne-azide cycloaddition, Diels-Alder cycloadditions, and thiol-click coupling.
NASA Astrophysics Data System (ADS)
Pszenny, A.; Cotter, K.; Deegan, B.; Fischer, E.; Johnson, D.
2007-12-01
PM2.5 aerosol was sampled over nominal 3-hour intervals at the head of Zuma Beach in Malibu, California (USA) from 6 to 24 October 2006 by filtration at 1.13 m3 min-1 (STP) through 20 x 25 cm cellulose fiber (Whatman 41) filters that had been rinsed with deionized water (DIW). Exposed filters were removed from support cartridges as soon as possible after retrieval (usually within 2 hours), immediately sealed in clean polyethylene bags, and stored frozen until further processing. Following the field campaign one quarter of each filter was pressed into a pellet (2.0 cm diameter x 0.5 cm thick) and analyzed by neutron activation for total concentrations of I and several other trace elements. Our preliminary analyses indicate that sodium and iodine show a clear diel variation characterized by higher concentrations from late morning to early evening. We hypothesize that this diel variability is related to a persistent land/sea breeze circulation associated with the nearby coastal region. Other elements are indicative of variability in other aerosol sources such as soil dust (Al, Mn) and fossil fuel combustion (V). Second quarters are currently being extracted in DIW and analyzed in two ways: 1) for iodide by ion chromatography, and 2) for inorganic iodine in higher oxidation states (i.e., V to 0) by chemical reduction with ascorbic acid followed by determination of iodide by ion chromatography. Results of the trace element and speciated iodine analyses will be presented.
Peng, Jing; Cao, Zhen-Dong; Fu, Shi-Jian
2014-10-01
We investigated the effects of constant and diel-fluctuating temperature acclimation on the thermal tolerance, swimming capacity, specific dynamic action (SDA) and growth performance of juvenile Chinese bream (Parabramis pekinensis). The critical thermal maxima (CTmax), critical thermal minima (CTmin), lethal thermal maxima (LTmax), lethal thermal minima (LTmin), critical swimming speed (Ucrit) and fast-start escape response after 30 d acclimation to three constant temperatures (15, 20 and 25 °C) and one diel-fluctuating temperature (20±5 °C) were measured. In addition, feeding rate (FR), feeding efficiency (FE) and specific growth rate (SGR) were measured. The diel-fluctuating temperature group showed lower CTmin than the 20 °C group but a similar CTmax, indicating a wider thermal scope. SDA linearly increased with the temperature. Temperature variation between 20 and 25 °C had little effect on either swimming or growth performance. However, fish in the 15 °C group exhibited much poorer swimming and growth performance than those in the 20 °C group. Ucrit decreased slightly under low acclimation temperature due to the pronounced improvement in swimming efficiency under cold temperature. Fish in the diel-fluctuating temperature group fed more but exhibited similar SGR compared to 20 °C group, possibly due in part to an increase in energy expenditure to cope with the temperature fluctuation. The narrower thermal scope and lower CTmax of Chinese bream together with the conservation of CTmax with temperature acclimation, suggests that local water temperature elevations may have more profound effects on Chinese bream than on other fish species in the Three Gorges Reservoir. Copyright © 2014 Elsevier Inc. All rights reserved.
Grantz, D.A.
2013-01-01
Plant injury by ozone (O3) occurs in three stages, O3 entrance through stomata, overcoming defences, and attack on bioreceptors. Concentration, deposition, and uptake of O3 are accessible by observation and modelling, while injury can be assessed visually or through remote sensing. However, the relationship between O3 metrics and injury is confounded by variation in sensitivity to O3. Sensitivity weighting parameters have previously been assigned to different plant functional types and growth stages, or by differentially weighting O3 concentrations, but diel and seasonal variability have not been addressed. Here a plant sensitivity parameter (S) is introduced, relating injury to O3 dose (uptake) using three independent injury endpoints in the crop species, Pima cotton (Gossypium barbadense). The diel variability of S was determined by assessment at 2h intervals. Pulses of O3 (15min) were used to assess passive (constitutive) defence mechanisms and dose was used rather than concentration to avoid genetic or environmental effects on stomatal regulation. A clear diel trend in S was apparent, with maximal sensitivity in mid-afternoon, not closely related to gas exchange, whole leaf ascorbate, or total antioxidant capacity. This physiologically based sensitivity parameter provides a novel weighting factor to improve modelled relationships between either flux or exposure to O3, and O3 impacts. This represents a substantial improvement over concentration- or phenology-based weighting factors currently in use. Future research will be required to characterize the variability and metabolic drivers of diel changes in S, and the performance of this parameter in prediction of O3 injury. PMID:23404900
Horning, M; Trillmich, F
1999-01-01
In our study of the development of diving in Galápagos fur seals, we analysed changes in diving activity and body mass trends over the lunar cycle. Based on previously observed lunar cycles in colony attendance patterns, we hypothesized a greater impact of prey migrations of deep scattering layer organisms on younger fur seals. Using electronic dive recorders, we determined that seals dived less and deeper on moonlit nights than at new moon, and incurred body mass losses. These changes in foraging over the lunar cycle correlate with the suppression of the vertical migration of prey by lunar light. All effects were more pronounced in juveniles than adult females, with greater relative mass loss during full moon, which must (i) negatively affect long-term juvenile growth rates, (ii) lengthen periods of maternal dependence, and (iii) contribute to the lowest reproductive rate reported for seals. This underlines the importance of studying ontogeny in order to understand life histories, and for determining the susceptibility of animal populations to fluctuations in food availability. PMID:10406130
ERIC Educational Resources Information Center
Weizman, Haim; Nielsen, Christian; Weizman, Or S.; Nemat-Nasser, Sia
2011-01-01
This laboratory experiment exposes students to the chemistry of self-healing polymers based on a Diels-Alder reaction. Students accomplish a multistep synthesis of a monomer building block and then polymerize it to form a cross-linked polymer. The healing capability of the polymer is verified by differential scanning calorimetry (DSC) experiments.…
Gärtner, Martin; Satyanarayana, Gedu; Förster, Sebastian; Helmchen, Günter
2013-01-02
Short and concise syntheses of the hexahydroindene cores of the antibiotics indanomycin (X-14547 A) and stawamycin are presented. Key methods used are an asymmetric iridium-catalyzed allylic alkylation, a modified Julia olefination, a Suzuki-Miyaura coupling, and an intramolecular Diels-Alder reaction. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Processing Conjugated-Diene-Containing Polymers
NASA Technical Reports Server (NTRS)
Bell, Vernon L.; Havens, Stephen J.
1987-01-01
Diels-Alder reaction used to cross-linked thermoplastics. Process uses Diels-Alder reaction to cross-link and/or extend conjugated-diene-containing polymers by reacting them with bis-unsaturated dienophiles results in improved polymer properties. Quantities of diene groups required for cross-linking varies from very low to very high concentrations. Process also used to extend, or build up molecular weights of, low-molecular-weight linear polymers with terminal conjugated dienic groups.
Fast Hetero-Diels-Alder Reactions Using 4-Phenyl-1,2,4-Triazoline-3,5-Dione (PTAD) as the Dienophile
ERIC Educational Resources Information Center
Celius, Tevye C.
2010-01-01
A hetero-Diels-Alder reaction that proceeds rapidly and only requires a simple filtration to purify the product is presented. The dienophile, 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD), is prepared by the heterogeneous oxidation of 4-phenylurazole by the bromenium ion, Br[superscript +], generated in situ by the oxidation of potassium bromide by…
R. F. Thurow
1997-01-01
Underwater observations were used to describe habitat use and diel behavior of juvenile bull trout (Salvelinus confluentus) at the onset of winter (0.8°C) in a second-order central Idaho stream. All fish observed during daytime counts were concealed beneath "home stones" (mean dimensions 32.3 by 21.9 cm) in primarily pool and run habitats. Focal point depths...
Liu, Yankai; Nappi, Manuel; Escudero-Adán, Eduardo C; Melchiorre, Paolo
2012-03-02
Expanding upon the recently developed aminocatalytic asymmetric indole-2,3-quinodimethane strategy, a straightforward synthesis of structurally and stereochemically complex tetrahydrocarbazoles has been devised. The chemistry's complexity-generating power was further harnessed by designing a multicatalytic, one-pot Diels-Alder/benzoin reaction sequence to stereoselectively access trans-fused tetracyclic indole-based compounds having four stereogenic centers with very high fidelity. © 2012 American Chemical Society
Silica-promoted Diels-Alder reactions in carbon dioxide from gaseous to supercritical conditions
DOE Office of Scientific and Technical Information (OSTI.GOV)
Weinstein, R.D.; Renslo, A.R.; Danheiser, R.L.
1999-04-15
Amorphous fumed silica (SiO{sub 2}) was shown to increase yields and selectivities of several Diels-Alder reactions in gaseous and supercritical CO{sub 2}. Pressure effects on the Diels-Alder reaction were explored using methyl vinyl ketone and penta-1,3-diene at 80 C. The selectivity of the reaction was not affected by pressure/density. As pressure was increased, the yield decreased. At the reaction temperature, adsorption isotherms at various pressures were obtained for the reactants and the Diels-Alder adduct. As expected when pressure is increased, the ratio of the amount of reactants adsorbed to the amount of reactants in the fluid phase decreases, thus causingmore » the yield to decrease. The Langmuir adsorption model fit the adsorption data. The Langmuir equilibrium partitioning constants all decreased with increasing pressure. The effect of temperature on adsorption was experimentally determined and traditional heats of adsorption were calculated. However, since supercritical CO{sub 2} is a highly compressible fluid, it is logical to examine the effect of temperature at constant density. In this case, entropies of adsorption were obtained. The thermodynamic properties that influence the real enthalpy and entropy of adsorption were derived. Methods of doping the silica and improving yields and selectivities were also explored.« less
Drivers of Variability of Diel-Cycling and Episodic Hypoxia In ...
Eutrophication of coastal ecosystems is a longstanding environmental concern, exacerbated by population growth and associated nutrient pollution, and ultimately resulting in increased incidence of hypoxia. Shallow and highly productive estuaries and embayments are particularly susceptible to diel-cycling hypoxia, associated with day-night cycles of production and respiration, which can cause extreme excursions in dissolved oxygen (DO) concentrations from anoxia to super-saturation within a single day. Diel oxygen dynamics in these systems are complex, and may be influenced by wind forcing, vertical and horizontal mixing, variation in freshwater inflow, cloud cover, and temperature. To better understand the environmental drivers of periodic hypoxia, this study examined four northern Gulf of Mexico Estuaries (Weeks Bay, AL; Wolf Bay, AL; Fowl River, AL; and St. Louis Bay, MS). Dissolved oxygen varied strongly on a diel basis in all four systems, with periods of sustained low oxygen (>24 h) observed in both Weeks Bay and Wolf Bay. The duration and persistence of hypoxia further varied in response to changing salinity regimes and regional weather. These results underscore the dynamic nature of hypoxia in shallow estuarine systems, and highlight the importance of combining fixed site continuous monitoring data with spatial hydrographic surveys to accurately resolve DO dynamics. This abstract is submitted for presentation at the CERF conference held Nov 8-12 in Oregon
Schotes, Christoph; Mezzetti, Antonio
2011-01-01
We report here dicationic ruthenium PNNP complexes that promote the enantioselective Diels-Alder reaction of alpha-methylene beta-ketoesters with various dienes. Complex [Ru(OEt2)2(PNNP)](PF6)2, formed in situ from [RuCl2,(PNNP)] and (Et3O)PF6 (2 equiv.), catalyzes the Diels-Alder reaction of such unsaturated beta-ketoesters to give novel alkoxycarbonyltetrahydro-1-indanone derivatives (nine examples) with up to 93% ee. The crystal structure of the substrate-catalyst adduct shows that the lower face of the substrate is shielded by a phenyl ring of the PNNP ligand, which accounts for the high enantioselectivity. The attack of the diene from the open re enantioface of the unsaturated beta-ketoester is consistent with the absolute configuration of the product. A useful application of this method is the reaction with Dane's diene to give estrone derivatives with up to 99% ee and an ester-exo:endo ratio of up to 145:1 (after recrystallization). Besides the enantioselective formation of all-carbon quaternary centers, this methodology is notable because unsaturated beta-ketoesters have been rarely used in Diels-Alder reactions. Furthermore, enantiomerically pure estrone derivatives are interesting in view of their potential applications, including the treatment of breast cancer.
Diel shifts in the structure and function of nearshore estuarine fish communities.
Yeoh, D E; Valesini, F J; Hallett, C S; Abdo, D A; Williams, J
2017-04-01
Day-night shifts in the nearshore fish fauna of a temperate microtidal estuary were assessed using a holistic suite of structural and functional community attributes. Mean fish species richness and diversity (taxonomic distinctness) were higher at night across all regions of the estuary and seasons, concurring with the findings of numerous comparable studies reviewed worldwide, while the diel period in which mean abundance was higher varied among seasons. Likewise, species and functional guild compositions (the latter based on feeding modes and habitat use) both differed significantly between day and night, with the extent of the diel shift again varying seasonally. Daytime fish communities were characterized by higher abundances of Atherinidae, Sillaginidae and Mugilidae, while Gobiidae were far more abundant at night. Marked shifts in size composition were also evident, with smaller fishes (<100 mm total length, L T ) being more prevalent during the day and larger fishes (≥200 mm L T ) proportionally more abundant at night. The above diel shifts were feasibly related to a range of predator-prey interactions and feeding-related movements, namely a nocturnal decrease in top-order avian piscivory coupled with an increase in invertebrate prey availability, resulting in changes in the presence and catchability of certain fish species in shallow estuarine waters. © 2016 The Fisheries Society of the British Isles.
Transcript, protein and metabolite temporal dynamics in the CAM plant Agave
Abraham, Paul E.; Yin, Hengfu; Borland, Anne M.; ...
2016-11-21
Already a proven mechanism for drought resilience, crassulacean acid metabolism (CAM) is a specialized type of photosynthesis that maximizes water-use efficiency (WUE) via an inverse (compared to C 3 and C 4 photosynthesis-performing species) day/night pattern of stomatal closure/opening to shift CO 2 uptake to the night, when evapotranspiration rates are low. A systems-level understanding of temporal molecular and metabolic controls is needed to define the cellular behavior that underpins CAM. Here, we report high-resolution temporal behaviors of transcript, protein and metabolite abundances across a CAM diel cycle and, where applicable, compare those observations to the well-established C 3 modelmore » plant, Arabidopsis thaliana. A mechanistic finding that emerged is that CAM operates with a diel redox poise that is shifted relative to that in Arabidopsis thaliana. Moreover, we identified widespread rescheduled expression of genes associated with signal transduction mechanisms that regulate stomatal opening/closing. Controlled production and degradation of transcripts and proteins represents a timing mechanism by which to regulate cellular function, yet how this molecular timekeeping regulates CAM physiology remains unclear. In this paper, we provide new insights into complex post-transcriptional and -translational hierarchies that govern CAM in Agave. These data sets together provide a resource to inform efforts to engineer more water-use efficient CAM pathway traits into economically valuable C 3 crops.« less
Transcript, protein and metabolite temporal dynamics in the CAM plant Agave
DOE Office of Scientific and Technical Information (OSTI.GOV)
Abraham, Paul E.; Yin, Hengfu; Borland, Anne M.
Already a proven mechanism for drought resilience, crassulacean acid metabolism (CAM) is a specialized type of photosynthesis that maximizes water-use efficiency (WUE) via an inverse (compared to C 3 and C 4 photosynthesis-performing species) day/night pattern of stomatal closure/opening to shift CO 2 uptake to the night, when evapotranspiration rates are low. A systems-level understanding of temporal molecular and metabolic controls is needed to define the cellular behavior that underpins CAM. Here, we report high-resolution temporal behaviors of transcript, protein and metabolite abundances across a CAM diel cycle and, where applicable, compare those observations to the well-established C 3 modelmore » plant, Arabidopsis thaliana. A mechanistic finding that emerged is that CAM operates with a diel redox poise that is shifted relative to that in Arabidopsis thaliana. Moreover, we identified widespread rescheduled expression of genes associated with signal transduction mechanisms that regulate stomatal opening/closing. Controlled production and degradation of transcripts and proteins represents a timing mechanism by which to regulate cellular function, yet how this molecular timekeeping regulates CAM physiology remains unclear. In this paper, we provide new insights into complex post-transcriptional and -translational hierarchies that govern CAM in Agave. These data sets together provide a resource to inform efforts to engineer more water-use efficient CAM pathway traits into economically valuable C 3 crops.« less
The Circadian Clock Modulates Global Daily Cycles of mRNA Ribosome Loading[OPEN
Missra, Anamika; Ernest, Ben; Jia, Qidong; Ke, Kenneth
2015-01-01
Circadian control of gene expression is well characterized at the transcriptional level, but little is known about diel or circadian control of translation. Genome-wide translation state profiling of mRNAs in Arabidopsis thaliana seedlings grown in long day was performed to estimate ribosome loading per mRNA. The experiments revealed extensive translational regulation of key biological processes. Notably, translation of mRNAs for ribosomal proteins and mitochondrial respiration peaked at night. Central clock mRNAs are among those subject to fluctuations in ribosome loading. There was no consistent phase relationship between peak translation states and peak transcript levels. The overlay of distinct transcriptional and translational cycles can be expected to alter the waveform of the protein synthesis rate. Plants that constitutively overexpress the clock gene CCA1 showed phase shifts in peak translation, with a 6-h delay from midnight to dawn or from noon to evening being particularly common. Moreover, cycles of ribosome loading that were detected under continuous light in the wild type collapsed in the CCA1 overexpressor. Finally, at the transcript level, the CCA1-ox strain adopted a global pattern of transcript abundance that was broadly correlated with the light-dark environment. Altogether, these data demonstrate that gene-specific diel cycles of ribosome loading are controlled in part by the circadian clock. PMID:26392078
Tamarix transpiration along a semiarid river has negligible impact on water resources
NASA Astrophysics Data System (ADS)
McDonald, Alyson K.; Wilcox, Bradford P.; Moore, Georgianne W.; Hart, Charles R.; Sheng, Zhuping; Owens, M. Keith
2015-07-01
The proliferation of saltcedar (Tamarix spp.) along regulated rivers in the western United States has transformed riparian plant communities. It is commonly assumed that transpiration by these alien plants has led to large losses of water that would otherwise contribute to streamflow. Control of saltcedar, therefore, has been considered a viable strategy for conserving water and increasing streamflow in these regions. In an effort to better understand the linkage between transpiration by saltcedar and streamflow, we monitored transpiration, stream stage, and groundwater elevations within a saltcedar stand along the Pecos River during June 2004. Transpiration, as determined by sap flow measurements, exhibited a strong diel pattern; stream stage did not. Diel fluctuations in groundwater levels were observed, but only in one well, which was located in the center of the saltcedar stand. In that well, the correlation between maximal transpiration and minimal groundwater elevation was weak (R2 = 0.16). No effects of transpiration were detected in other wells within the saltcedar stand, nor in the stream stage. The primary reason, we believe, is that the saltcedar stand along this reach of the Pecos River has relatively low sapwood area and a limited spatial extent resulting in very low transpiration compared with the stream discharge. Our results are important because they provide a mechanistic explanation for the lack of increase in streamflow following large-scale control of invasive trees along semiarid rivers.
Seasonal and diel patterns of larval fish drift in a western South Carolina swamp
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kissick, L.A.; Paller, M.H.; Heuer, J.H.
1988-01-01
Fish larvae were collected weekly during 1986-1987 from the lower 3 km of Steel Creek (Barnwell County), a riverine swamp, to assess reproduction in this rarely studied habitat type. In 1987, larvae appeared in the following order and abundance (as a percentage of the total diural density): blackbanded darter Percina nigromaculatus (3%) and other darters Etheostoma spp. (32%); pirate perch Aphredoderus sayanus (NA); pygmy sunfish Elassoma spp. (7%); chubsuckers Erimyson spp. (13%); bluespotted sunfish Enneacanthus gloriosus (16%); bluegill Lepomis macrochirus (1%), redbreast sunfish L. auritus (<1%), brook silverside Labidesthes sicculus (6%) and ironcolor shiner Notropis chalybaeus (8%); warmouth L. gulosusmore » (8%); spotted sunfish L. punctatus (NA). Unidentified cyprinids (2%), centrarchids (2%) and miscellaneous species (3%) were collected throughout the study period. Monthly diel collections showed that drift densities of chubsuckers, cyprinids, Etheostoma spp., bluegill and pygmy sunfish increased 41 to 160X after sundown; pirate perch and spotted sunfish were collected only at night. Swamp densities peaked during 2000-0159 h (111.5 per 100m), whereas densities in the channel that drained the swamp into the Savannah River peaked during 0200-0759 h (38.7). The later peak in the channel was attributed to larvae that had drifted from the swamp and were essentially lost from the system. 4 figs., 1 tab.« less
Aldous, Sophia H.; Weise, Sean E.; Sharkey, Thomas D.; Waldera-Lupa, Daniel M.; Stühler, Kai; Mallmann, Julia; Groth, Georg; Gowik, Udo; Westhoff, Peter; Arsova, Borjana
2014-01-01
The key enzyme for C4 photosynthesis, Phosphoenolpyruvate Carboxylase (PEPC), evolved from nonphotosynthetic PEPC found in C3 ancestors. In all plants, PEPC is phosphorylated by Phosphoenolpyruvate Carboxylase Protein Kinase (PPCK). However, differences in the phosphorylation pattern exist among plants with these photosynthetic types, and it is still not clear if they are due to interspecies differences or depend on photosynthetic type. The genus Flaveria contains closely related C3, C3-C4 intermediate, and C4 species, which are evolutionarily young and thus well suited for comparative analysis. To characterize the evolutionary differences in PPCK between plants with C3 and C4 photosynthesis, transcriptome libraries from nine Flaveria spp. were used, and a two-member PPCK family (PPCKA and PPCKB) was identified. Sequence analysis identified a number of C3- and C4-specific residues with various occurrences in the intermediates. Quantitative analysis of transcriptome data revealed that PPCKA and PPCKB exhibit inverse diel expression patterns and that C3 and C4 Flaveria spp. differ in the expression levels of these genes. PPCKA has maximal expression levels during the day, whereas PPCKB has maximal expression during the night. Phosphorylation patterns of PEPC varied among C3 and C4 Flaveria spp. too, with PEPC from the C4 species being predominantly phosphorylated throughout the day, while in the C3 species the phosphorylation level was maintained during the entire 24 h. Since C4 Flaveria spp. evolved from C3 ancestors, this work links the evolutionary changes in sequence, PPCK expression, and phosphorylation pattern to an evolutionary phase shift of kinase activity from a C3 to a C4 mode. PMID:24850859
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.
Structural basis for Diels-Alder ribozyme-catalyzed carbon-carbon bond formation
Serganov, Alexander; Keiper, Sonja; Malinina, Lucy; Tereshko, Valentina; Skripkin, Eugene; Höbartner, Claudia; Polonskaia, Anna; Phan, Anh Tuân; Wombacher, Richard; Micura, Ronald; Dauter, Zbigniew; Jäschke, Andres; Patel, Dinshaw J
2015-01-01
The majority of structural efforts addressing RNA’s catalytic function have focused on natural ribozymes, which catalyze phosphodiester transfer reactions. By contrast, little is known about how RNA catalyzes other types of chemical reactions. We report here the crystal structures of a ribozyme that catalyzes enantioselective carbon-carbon bond formation by the Diels-Alder reaction in the unbound state and in complex with a reaction product. The RNA adopts a λ-shaped nested pseudoknot architecture whose preformed hydrophobic pocket is precisely complementary in shape to the reaction product. RNA folding and product binding are dictated by extensive stacking and hydrogen bonding, whereas stereoselection is governed by the shape of the catalytic pocket. Catalysis is apparently achieved by a combination of proximity, complementarity and electronic effects. We observe structural parallels in the independently evolved catalytic pocket architectures for ribozyme- and antibody-catalyzed Diels-Alder carbon-carbon bond-forming reactions. PMID:15723077
Kalaoglu-Altan, Ozlem I; Sanyal, Rana; Sanyal, Amitav
2015-05-11
Fabrication of hydrophilic polymeric nanofibers that undergo facile and selective functionalization through metal catalyst-free Diels-Alder "click" reaction in aqueous environment is outlined. Electrospinning of copolymers containing an electron-rich furan moiety, hydrophobic methyl methacrylate units and hydrophilic poly(ethylene glycol)s as side chains provide specifically functionalizable yet antibiofouling fibers that remain stable in aqueous media due to appropriate hydrophobic hydrophilic balance. Efficient functionalization of these nanofibers is accomplished through the Diels-Alder reaction by exposing them to maleimide-containing molecules and ligands. Diels-Alder conjugation based functionalization is demonstrated through attachment of fluorescein-maleimide and a maleimide tethered biotin ligand. Biotinylated nanofibers were utilized to mediate immobilization of the protein streptavidin, as well as streptavidin coated quantum dots. Facile fabrication from readily available polymers and their effective functionalization under mild and reagent-free conditions in aqueous media make these "clickable" nanofibers attractive candidates as functionalizable scaffolds for various biomedical applications.
Johnson, James H.
2013-01-01
The habitat use, diet composition, and feeding periodicity of subyearling Atlantic salmon (Salmo salar) was examined during both day and night periods during summer in tributaries of Lake Ontario. The amount of cover used was the major habitat variable that differed between day and night periods in both streams. At night subyearling Atlantic salmon were associated with significantly less cover than during the day. Principal Component Analysis showed that habitat selection of subyearling Atlantic salmon was more pronounced during the day in both streams and that salmon in Orwell Brook exhibited more diel variability in habitat use than salmon in Trout Brook. Subyearling salmon fed primarily from the benthic substrate on baetids, chironomids, and leptocerids. There was a substantial amount of diel variation in diet composition with peak feeding occurring from 0400 h to 0800 h on July 21–22, 2008.
The hexadehydro-Diels-Alder reaction.
Hoye, Thomas R; Baire, Beeraiah; Niu, Dawen; Willoughby, Patrick H; Woods, Brian P
2012-10-11
Arynes (aromatic systems containing, formally, a carbon-carbon triple bond) are among the most versatile of all reactive intermediates in organic chemistry. They can be 'trapped' to give products that are used as pharmaceuticals, agrochemicals, dyes, polymers and other fine chemicals. Here we explore a strategy that unites the de novo generation of benzynes-through a hexadehydro-Diels-Alder reaction-with their in situ elaboration into structurally complex benzenoid products. In the hexadehydro-Diels-Alder reaction, a 1,3-diyne is engaged in a [4+2] cycloisomerization with a 'diynophile' to produce the highly reactive benzyne intermediate. The reaction conditions for this simple, thermal transformation are notable for being free of metals and reagents. The subsequent and highly efficient trapping reactions increase the power of the overall process. Finally, we provide examples of how this de novo benzyne generation approach allows new modes of intrinsic reactivity to be revealed.
NASA Astrophysics Data System (ADS)
Della Rosa, Claudia D.; Mancini, Pedro M. E.; Kneeteman, Maria N.; Lopez Baena, Anna F.; Suligoy, Melisa A.; Domingo, Luis R.
2015-01-01
The reactions between 2- and 3-nitrobenzothiophenes with three dienes of different nucleophilicity, 1-methoxy-3-trimethylsilyloxy-1,3-butadiene, 1-trimethylsilyloxy-1,3-butadiene and isoprene developed in anhydrous benzene and alternative under microwave irradiation with molecular solvents or in free solvent conditions, respectively, for produce dibenzothiophenes permit to conclude that both nitroheterocycles act as electrophile with the cited dienes. In the cases of the dienes 1-methoxy-3-trimethylsilyloxy-1,3-butadiene and 1-trimethylsilyloxy-1,3-butadiene which posses major nucleophilicity the observed product is the normal cycloaddition one. However when the diene is isoprene the product with both electrophiles follow the hetero Diels-Alder way. These reactions are considered polar cycloaddition reactions and the yields are reasonables. Moreover the polar Diels-Alder reactions of nitrobenzothiophenes with electron rich dienes 1-trimethylsilyloxy-1,3-butadiene have been theoretically studied using DFT methods.
van der Gracht, Anouk M F; de Geus, Mark A R; Camps, Marcel G M; Ruckwardt, Tracy J; Sarris, Alexi J C; Bremmers, Jessica; Maurits, Elmer; Pawlak, Joanna B; Posthoorn, Michelle M; Bonger, Kimberly M; Filippov, Dmitri V; Overkleeft, Herman S; Robillard, Marc S; Ossendorp, Ferry; van Kasteren, Sander I
2018-06-15
Activation of a cytotoxic T-cell is a complex multistep process, and tools to study the molecular events and their dynamics that result in T-cell activation in situ and in vivo are scarce. Here, we report the design and use of conditional epitopes for time-controlled T-cell activation in vivo. We show that trans-cyclooctene-protected SIINFEKL (with the lysine amine masked) is unable to elicit the T-cell response characteristic for the free SIINFEKL epitope. Epitope uncaging by means of an inverse-electron demand Diels-Alder (IEDDA) event restored T-cell activation and provided temporal control of T-cell proliferation in vivo.
Lopes, Susana M M; Novais, Juliana S; Costa, Dora C S; Castro, Helena C; Figueiredo, Agnes Marie S; Ferreira, Vitor F; Pinho E Melo, Teresa M V D; da Silva, Fernando de Carvalho
2018-01-01
The generation and reactivity of 3-triazolyl-nitrosoalkenes are reported for the first time. The study showed that hetero-Diels-Alder reaction of these heterodienes is an interesting synthetic strategy to functionalized 1,2,3-triazoles, including 1,2,3-triazolyl-pyrroles, 1,2,3-triazolyl-dipyrromethanes and 1,2,3-triazolyl-indoles. The evaluation of the antibacterial profile against Gram-positive and Gram-negative strains revealed the new 5,5'-diethyldipyrromethane bearing a side chain incorporating a triazole and oxime moieties. The antibacterial profile detected was within the Clinical and Laboratory Standard Institute (CLSI) range and against important Staphylococcus species including Methicillin-resistant strain (S. aureus ATCC 25923, S. epidermidis ATCC 12228 and S. simulans ATCC 27851 and MRSA). Interestingly, this new 1,2,3-triazole presented hemocompatibility and low in silico toxicity profile similar to antibiotics current in use. It also has an usual antibiofilm activity against MRSA, which reinforced its potential as a new antibacterial prototype. Copyright © 2017 Elsevier Masson SAS. All rights reserved.
Argon concentration time-series as a tool to study gas dynamics in the hyporheic zone.
Mächler, Lars; Brennwald, Matthias S; Kipfer, Rolf
2013-07-02
The oxygen dynamics in the hyporheic zone of a peri-alpine river (Thur, Switzerland), were studied through recording and analyzing the concentration time-series of dissolved argon, oxygen, carbon dioxide, and temperature during low flow conditions, for a period of one week. The argon concentration time-series was used to investigate the physical gas dynamics in the hyporheic zone. Differences in the transport behavior of heat and gas were determined by comparing the diel temperature evolution of groundwater to the measured concentration of dissolved argon. These differences were most likely caused by vertical heat transport which influenced the local groundwater temperature. The argon concentration time-series were also used to estimate travel times by cross correlating argon concentrations in the groundwater with argon concentrations in the river. The information gained from quantifying the physical gas transport was used to estimate the oxygen turnover in groundwater after water recharge. The resulting oxygen turnover showed strong diel variations, which correlated with the water temperature during groundwater recharge. Hence, the variation in the consumption rate was most likely caused by the temperature dependence of microbial activity.
Microhabitat and biology of Sphaerium striatinum in a central New York stream
Dittman, Dawn E.; Johnson, James H.; Nack, Christopher C.
2018-01-01
In many lotic systems, drastic declines in freshwater bivalve populations, including fingernail clams (Sphaeriidae), have created concerns about biodiversity and future ecosystem services. We examined the local occurrence of the historically common fingernail clam, Sphaerium striatinum, in a central New York stream. We sampled the density of sphaeriids and measured the associated habitat variables (substrate, depth, water flow) to test within-stream multivariate benthic microhabitat association. Size distribution, density, and diel feeding periodicity were measured as focal aspects of fingernail clam biology and ecology. S. striatinum tended to be found in microhabitats that had harder substrates and faster flow. The Labrador Creek fingernail clam local population had positive indicators (size distribution, density). There was significant diel periodicity in feeding behavior. The clams fed most actively during the 0400–0800 h periods. This kind of behavioral periodicity can indicate a significant ecological interaction between predators and bivalve prey. Increased understanding of the behavioral ecology of small native freshwater bivalves in an unimpacted headwater stream is a fundamental building block for development of overall ecological conservation goals for freshwater bivalves and their lotic habitats.
NASA Astrophysics Data System (ADS)
Kobari, Toru; Steinberg, Deborah K.; Ueda, Ai; Tsuda, Atsushi; Silver, Mary W.; Kitamura, Minoru
2008-07-01
To evaluate the impacts of ontogenetically (seasonally) migrating copepods on carbon transport to the mesopelagic zone, we investigated depth distribution, population structure, and feeding activity of the ontogentic copepod community in the western subarctic Pacific Ocean from day-night pairs of zooplankton samples down to 1000 m during the VERtical Transport In the Global Ocean (VERTIGO) program. Over the 31 July-16 August 2005 study period, the biomass of Neocalanus cristatus and Neocalanus plumchrus predominated in the near surface waters, while Neocalanus flemingeri was already dormant at depth. We observed a strong diel migration for Metridia pacifica, and a seasonal downward migration for Eucalanus bungii. Based on gut pigment analysis, ingestion rate of the copepod community was 214-375 mg C m -2 day -1, which was equal to 26-37% of the concurrent primary production. However, comparison of grazing estimated from gut pigments to calculated carbon demand of the copepod community indicates that phytoplankton comprised 37-59% of the ingested carbon. Thus, the copepod community appears to have also relied on detritus and microzooplankton for their nutrition, likely because primary production during this time was dominated by picophytoplankton too small to be grazed by these large copepods. Fecal pellet flux by the copepod community was estimated to account for 141-223% of the sedimentary particulate organic carbon (POC) flux at 150 m, suggesting considerable fragmentation and consumption of pellets in the upper layers. Fecal pellets alone were adequate to meet copepod carbon demand in the surface 0-150 m layer. Active carbon flux by diel migration of M. pacifica (respiration, egestion, and mortality) was 4-17 mg C m -2 day -1, equal to 6-44% of sedimentary POC flux at 150 m. Active carbon flux by N. flemingeri ontogenetic migration (i.e., respiration and mortality at depth) contributed 246 mg C m -2 year -1, equal to 9% of sedimentary POC flux at 1000 m. The imminent downward migration of N. cristatus and N. plumchrus would lead to an additional ontogenetic carbon flux on the order of 1719 mg C m -2 year -1. Copepod fecal pellet transport and active transport by diel and ontogenetic migration are thus important carbon fluxes during a season dominated by small phytoplankton, and ontogenetic migrants in the subarctic Pacific Ocean play a relatively more important role in active carbon flux compared with other open-ocean regions.
Shchepin, Roman; Möller, Matias N; Kim, Hye-young H; Hatch, Duane M; Bartesaghi, Silvina; Kalyanaraman, Balaraman; Radi, Rafael; Porter, Ned A
2010-12-15
Free radical co-oxidation of polyunsaturated lipids with tyrosine or phenolic analogues of tyrosine gave rise to lipid peroxide-tyrosine (phenol) adducts in both aqueous micellar and organic solutions. The novel adducts were isolated and characterized by 1D and 2D NMR spectroscopy as well as by mass spectrometry (MS). The spectral data suggest that the polyunsaturated lipid peroxyl radicals give stable peroxide coupling products exclusively at the para position of the tyrosyl (phenoxy) radicals. These adducts have characteristic (13)C chemical shifts at 185 ppm due to the cross-conjugated carbonyl of the phenol-derived cyclohexadienone. The primary peroxide adducts subsequently undergo intramolecular Diels-Alder (IMDA) cyclization, affording a number of diastereomeric tricyclic adducts that have characteristic carbonyl (13)C chemical shifts at ~198 ppm. All of the NMR HMBC and HSQC correlations support the structure assignments of the primary and Diels-Alder adducts, as does MS collision-induced dissociation data. Kinetic rate constants and activation parameters for the IMDA reaction were determined, and the primary adducts were reduced with cuprous ion to give a phenol-derived 4-hydroxycyclohexa-2,5-dienone. No products from adduction of peroxyls at the phenolic ortho position were found in either the primary or cuprous reduction product mixtures. These studies provide a framework for understanding the nature of lipid-protein adducts formed by peroxyl-tyrosyl radical-radical termination processes. Coupling of lipid peroxyl radicals with tyrosyl radicals leads to cyclohexenone and cyclohexadienone adducts, which are of interest in and of themselves since, as electrophiles, they are likely targets for protein nucleophiles. One consequence of lipid peroxyl reactions with tyrosyls may therefore be protein-protein cross-links via interprotein Michael adducts.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Schlatterer, Joerg C., E-mail: joerg.schlatterer@einstein.yu.edu; Wieder, Matthew S.; Jones, Christopher D.
2012-08-24
Highlights: Black-Right-Pointing-Pointer RNA structure is mapped by pyrite mediated {sup {center_dot}}OH footprinting. Black-Right-Pointing-Pointer Repetitive experiments can be done in a powdered pyrite filled cartridge. Black-Right-Pointing-Pointer High {sup {center_dot}}OH reactivity of nucleotides imply dynamic role in Diels-Alderase catalysis. -- Abstract: In RNA, function follows form. Mapping the surface of RNA molecules with chemical and enzymatic probes has revealed invaluable information about structure and folding. Hydroxyl radicals ({sup {center_dot}}OH) map the surface of nucleic acids by cutting the backbone where it is accessible to solvent. Recent studies showed that a microfluidic chip containing pyrite (FeS{sub 2}) can produce sufficient {sup {center_dot}}OH tomore » footprint DNA. The 49-nt Diels-Alder RNA enzyme catalyzes the C-C bond formation between a diene and a dienophile. A crystal structure, molecular dynamics simulation and atomic mutagenesis studies suggest that nucleotides of an asymmetric bulge participate in the dynamic architecture of the ribozyme's active center. Of note is that residue U42 directly interacts with the product in the crystallized RNA/product complex. Here, we use powdered pyrite held in a commercially available cartridge to footprint the Diels-Alderase ribozyme with single nucleotide resolution. Residues C39 to U42 are more reactive to {sup {center_dot}}OH than predicted by the solvent accessibility calculated from the crystal structure suggesting that this loop is dynamic in solution. The loop's flexibility may contribute to substrate recruitment and product release. Our implementation of pyrite-mediated {sup {center_dot}}OH footprinting is a readily accessible approach to gleaning information about the architecture of small RNA molecules.« less
Shchepin, Roman; Möller, Matias N.; Kim, Hye-young H.; Hatch, Duane M.; Bartesaghi, Silvina; Kalyanaraman, Balaraman; Radi, Rafael
2013-01-01
Free radical co-oxidation of polyunsaturated lipids with tyrosine or phenolic analogs of tyrosine gave rise to lipid peroxide-tyrosine (phenol) adducts in both aqueous micellar and organic solutions. The novel adducts were isolated and characterized by 1D and 2D NMR as well as by mass spectrometry. The spectral data suggest that the polyunsaturated lipid peroxyl radicals give stable peroxide coupling products exclusively at the para position of the tyrosyl (phenoxy) radicals. These adducts have characteristic 13C chemical shifts at 185 ppm due to the cross-conjugated carbonyl of the phenol-derived cyclohexadienone. The primary peroxide adducts subsequently undergo intramolecular Diels-Alder (IMDA) cyclization, affording a number of diastereomeric tricyclic adducts that have characteristic carbonyl 13C chemical shifts at ~198 ppm. All NMR HMBC and HSQC correlations support the structure assignment of the primary and Diels-Alder adducts, as does MS collision induced dissociation. Kinetic rate constants and activation parameters for the IMDA reaction were determined and the primary adducts were reduced with cuprous ion giving a phenol-derived 4-hydroxycyclohexa-2,5-dienone. No products from adduction of peroxyls at the phenolic ortho position were found either in the primary or the cuprous reduction product mixtures. These studies provide a framework for understanding the nature of lipid-protein adducts formed by peroxyl-tyrosyl radical-radical termination processes. Coupling of lipid peroxyl radicals with tyrosyl radicals leads to cyclohexenone and cyclohexadienone adducts which are of interest in and of themselves since, as electrophiles, they are likely targets for protein nucleophiles. One consequence of lipid peroxyl reactions with tyrosyls may therefore be protein-protein crosslinks via interprotein Michael adducts. PMID:21090613
Water Quality Conditions in Upper Klamath and Agency Lakes, Oregon, 2005
Hoilman, Gene R.; Lindenberg, Mary K.; Wood, Tamara M.
2008-01-01
During June-October 2005, water quality data were collected from Upper Klamath and Agency Lakes in Oregon, and meteorological data were collected around and within Upper Klamath Lake. Data recorded at two continuous water quality monitors in Agency Lake showed similar temperature patterns throughout the field season, but data recorded at the northern site showed more day-to-day variability for dissolved oxygen concentration and saturation after late June and more day-to-day variability for pH and specific conductance values after mid-July. Data recorded from the northern and southern parts of Agency Lake showed more comparable day-to-day variability in dissolved oxygen concentrations and pH from September through the end of the monitoring period. For Upper Klamath Lake, seasonal (late July through early August) lows of dissolved oxygen concentrations and saturation were coincident with a seasonal low of pH values and seasonal highs of ammonia and orthophosphate concentrations, specific conductance values, and water temperatures. Patterns in these parameters, excluding water temperature, were associated with bloom dynamics of the cyanobacterium (blue-green alga) Aphanizomenon flos-aquae in Upper Klamath Lake. In Upper Klamath Lake, water temperature in excess of 28 degrees Celsius (a high stress threshold for Upper Klamath Lake suckers) was recorded only once at one site during the field season. Large areas of Upper Klamath Lake had periods of dissolved oxygen concentration of less than 4 milligrams per liter and pH value greater than 9.7, but these conditions were not persistent throughout days at most sites. Dissolved oxygen concentrations in Upper Klamath Lake on time scales of days and months appeared to be influenced, in part, by bathymetry and prevailing current flow patterns. Diel patterns of water column stratification were evident, even at the deepest sites. This diel pattern of stratification was attributable to diel wind speed patterns and the shallow nature of most of Upper Klamath Lake. Timing of the daily extreme values of dissolved oxygen concentration, pH, and water temperature was less distinct with increased water column depth. Chlorophyll a concentrations varied spatially and temporally throughout Upper Klamath Lake. Location greatly affected algal concentrations, in turn affecting nutrient and dissolved oxygen concentrations - some of the highest chlorophyll a concentrations were associated with the lowest dissolved oxygen concentrations and the highest un-ionized ammonia concentrations. The occurrence of the low dissolved oxygen and high un-ionized ammonia concentrations coincided with a decline in algae resulting from cell death, as measured by concentrations of chlorophyll a. Dissolved oxygen production rates in experiments were as high as 1.47 milligrams of oxygen per liter per hour, and consumption rates were as much as -0.73 milligrams of oxygen per liter per hour. Dissolved oxygen consumption rates measured in this study were comparable to those measured in a 2002 Upper Klamath Lake study, and a higher rate of dissolved oxygen consumption was recorded in dark bottles positioned higher in the water column. Data, though inconclusive, indicated that a decreasing trend of dissolved oxygen productivity through July could have contributed to the decreasing dissolved oxygen concentrations and percent saturation recorded in Upper Klamath Lake during this time. Phytoplankton self-shading was evident from a general inverse relation between depth of photic zone and chlorophyll a concentrations. This shading caused net dissolved oxygen consumption during daylight hours in lower parts of the water column that would otherwise have been in the photic zone. Meteorological data collected in and around Upper Klamath Lake showed that winds were likely to come from a broad range of westerly directions in the northern one-third of the lake, but tended to come from a narrow range of northwesterly directions
Helble, Tyler A; D'Spain, Gerald L; Campbell, Greg S; Hildebrand, John A
2013-11-01
This paper demonstrates the importance of accounting for environmental effects on passive underwater acoustic monitoring results. The situation considered is the reduction in shipping off the California coast between 2008-2010 due to the recession and environmental legislation. The resulting variations in ocean noise change the probability of detecting marine mammal vocalizations. An acoustic model was used to calculate the time-varying probability of detecting humpback whale vocalizations under best-guess environmental conditions and varying noise. The uncorrected call counts suggest a diel pattern and an increase in calling over a two-year period; the corrected call counts show minimal evidence of these features.
National Research Council Resident Research Associateship (NRC-RRA) program
1988-08-01
Davis, C. J. Dymek, J. J. P. Stewart, H. P. Clark, W. J. Lauderdale, J. Am. Chem. Soc., 107, 5041-5046 (1985). 7. "Mechanism of the Diels - Alder ...Package" Dewar Research Group and J. J. P. Stewart, Quantum Chemistry Program Exchange, no. 506, nn, nnn, (1986) 16. "Mechanism of the Diels - Alder ...Kvisle, 0. Nirisen, M. Ystenes, and H. A. Oye, Proceedings of 1986 International Symposium on Transition Metals Catalyzed Polymerizations, Institute of
The unexpected product of Diels-Alder reaction between "indanocyclon" and maleimide
NASA Astrophysics Data System (ADS)
Dobrowolski, Michał A.; Roszkowski, Piotr; Struga, Marta; Szulczyk, Daniel
2017-02-01
A heterocyclic compound commonly known as "indanocyclon" undergoes an unexpected Diels-Alder addition with maleimide. The resulting product has been isolated and characterized in order to get an information about its structure and possible mechanism of the reaction. Extensive comparison of single crystal properties of 3-(2,8-dioxo-1,3-diphenyl-2,8-dihydrocyclopenta[a]inden-8a(1H)-yl)pyrrolidine-2,5-dione and favorable product of the reaction has been also performed.
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.
Night sampling improves indices used for management of yellow perch in Lake Erie
Kocovsky, P.M.; Stapanian, M.A.; Knight, C.T.
2010-01-01
Catch rate (catch per hour) was examined for age-0 and age-1 yellow perch, Perca flavescens (Mitchill), captured in bottom trawls from 1991 to 2005 in western Lake Erie: (1) to examine variation of catch rate among years, seasons, diel periods and their interactions; and (2) to determine whether sampling during particular diel periods improved the management value of CPH data used in models to project abundance of age-2 yellow perch. Catch rate varied with year, season and the diel period during which sampling was conducted as well as by the interaction between year and season. Indices of abundance of age-0 and age-1 yellow perch estimated from night samples typically produced better fitting models and lower estimates of age-2 abundance than those using morning or afternoon samples, whereas indices using afternoon samples typically produced less precise and higher estimates of abundance. The diel period during which sampling is conducted will not affect observed population trends but may affect estimates of abundance of age-0 and age-1 yellow perch, which in turn affect recommended allowable harvest. A field experiment throughout western Lake Erie is recommended to examine potential benefits of night sampling to management of yellow perch. Published 2010. The article is a US Government work and is in the public domain in the USA.
Light-mediated Zn uptake in photosynthetic biofilm
Morris, J.M.; Farag, A.M.; Nimick, D.A.; Meyer, J.S.
2006-01-01
Our experiments conducted under controlled laboratory conditions demonstrate diel uptake and release of zinc (Zn) in lab-cultured biofilm exposed to Zn concentrations that are present in some mining-impacted streams (1-2 mg Zn/l). Specifically, at constant pH, temperature, and aqueous Zn concentrations in the exposure water, biofilm accumulated Zn during the light periods of the photocycle and released Zn during the dark periods of the photocycle. The range of Zn uptake measured in biofilm during one light period in these laboratory experiments (0.6-8.3 mg Zn/g dw biofilm) encompassed the estimated Zn uptake (1.5-3.7 mg Zn/g dw biofilm) necessary to attribute aqueous diel Zn cycling in a mining-impacted stream in Montana (High Ore Creek) to uptake in biofilm. This is relevant to in situ studies of diel Zn cycling because we controlled three important parameters that naturally fluctuate daily in the field, thus demonstrating the potential for biofilm to remove large percentages of Zn from some mining-impacted streams. Researchers, modelers, regulators, and reclamation teams working in metals-contaminated streams should be aware of diel metal cycling, because the highest Zn concentrations (and therefore, perhaps the most toxic conditions) in the water column might occur at night, and the greatest exposure of grazers of phototrophs to dietborne Zn might occur during daylight hours. ?? Springer 2006.
NASA Astrophysics Data System (ADS)
Downs, C. M.; Krauss, K.; Kruse, S.
2017-12-01
The movement and storage of porewater salts is poorly understood in mangrove forests with limited surface water exchange between the forest and neighboring lagoon. These mangroves are often the most stressed, and have the most unfavorable salinity balance that often transition to mortality during extreme drought. A time-lapse resistivity survey was conducted in a stressed mangrove forest over a diel period. Resistivity is sensitive to the entire soil volume, including fine roots. The objective was to image changes in porewater salinity structures around both mangrove trees, where roots can be a prolific contributor to soil volume, and a salt pan with little or no vegetation. Throughout the diel period, salt pan conductivities remained relatively constant. The most significant temporal changes occur in the root zone around mangrove trees. Particularly interesting is a drop in resistivity (increased conductivity) at sunset when transpiration from individual trees decreases (or even ceases), potentially identifying a cumulative concentration of salts around the mangrove root zone after a full day of transpiration. The resistivity gradient decreases immediately after its peak at sunset, potentially identifying the consequences of hydraulic redistribution in diluting soils surrounding trees immediately after transpiration ceases. This is quicker than expected, and may imply a very strong and rapid eco-hydrological connection in the tree-facilitated salinity balance essential to their survival under the most salinity-stressed environments. At sunrise, resistivity increases, further suggesting dilution of salts via hydraulic redistribution of fresh water from the tree into the upper soil layers, or suggests an accumulation of salts within roots when presumably less water is moving through the trees. Repeated electric resistivity arrays provide spatial and temporal information about these salts and contribute to an overall understanding of how stressed mangrove forests behave. The mangrove ecophysiology literature has suggested that such a balance should exist between tree water use and soil salinity concentration. Here, we document the diel pattern from the perspective of the soil for the first time, but need more surveys to develop conclusive ecosystem level impacts.
Diel periodicity of Drosophila suzukii (Diptera: Drosophilidae) under field conditions
Evans, Richard K.; Toews, Michael D.
2017-01-01
Drosophila suzukii Matsumura (Diptera: Drosophilidae), an economically important pest of blueberry and other thin-skinned fruits, persists and prolifically reproduces under seemingly lethal climatic conditions in the field. However, behavioral and physiological mechanisms employed by D. suzukii to tolerate such extreme climatic conditions in the field are unknown. The primary objective of this project was to investigate diel periodicity of D. suzukii and their reproductive success under field conditions as related by climatic factors such as temperature and relative humidity. Results show that D. suzukii reproductive success was significantly higher during the night (including dawn and dusk periods) than the day in terms of oviposition, pupation, adult eclosion, and the number of progeny per female. Female D. suzukii reproductive success was not significantly different between specific regions of a blueberry bush in relation to the amount of shade provided by the canopy. Our studies indicate that D. suzukii flight activity is crepuscular and is sensitive to fluctuations in temperature and relative humidity. Results also suggest that the majority of fly activity during peak hours is concentrated in areas around the border and within the center of blueberry orchards with little activity in the surrounding wooded areas. These findings suggest that D. suzukii prefers microclimate with mild temperatures and high humidity, and does not function well when exposed to direct sunlight with extreme heat. The authors propose that D. suzukii management strategies should be implemented during the early morning and immediately before darkness to maximize efficacy. PMID:28187140
Nocturnality constrains morphological and functional diversity in the eyes of reef fishes.
Schmitz, Lars; Wainwright, Peter C
2011-11-19
Ambient light levels are often considered to drive the evolution of eye form and function. Diel activity pattern is the main mechanism controlling the visual environment of teleost reef fish, with day-active (diurnal) fish active in well-illuminated conditions, whereas night-active (nocturnal) fish cope with dim light. Physiological optics predicts several specific evolutionary responses to dim-light vision that should be reflected in visual performance features of the eye. We analyzed a large comparative dataset on morphological traits of the eyes in 265 species of teleost reef fish in 43 different families. The eye morphology of nocturnal reef teleosts is characterized by a syndrome that indicates better light sensitivity, including large relative eye size, high optical ratio and large, rounded pupils. Improved dim-light image formation comes at the cost of reduced depth of focus and reduction of potential accommodative lens movement. Diurnal teleost reef fish, released from the stringent functional requirements of dim-light vision have much higher morphological and optical diversity than nocturnal species, with large ranges of optical ratio, depth of focus, and lens accommodation. Physical characteristics of the environment are an important factor in the evolution and diversification of the vertebrate eye. Both teleost reef fish and terrestrial amniotes meet the functional requirements of dim-light vision with a similar evolutionary response of morphological and optical modifications. The trade-off between improved dim-light vision and reduced optical diversity may be a key factor in explaining the lower trophic diversity of nocturnal reef teleosts.
Large scale patterns in vertical distribution and behaviour of mesopelagic scattering layers
NASA Astrophysics Data System (ADS)
Klevjer, T. A.; Irigoien, X.; Røstad, A.; Fraile-Nuez, E.; Benítez-Barrios, V. M.; Kaartvedt., S.
2016-01-01
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.
Large scale patterns in vertical distribution and behaviour of mesopelagic scattering layers.
Klevjer, T A; Irigoien, X; Røstad, A; Fraile-Nuez, E; Benítez-Barrios, V M; Kaartvedt, S
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.
Kline, David I; Teneva, Lida; Hauri, Claudine; Schneider, Kenneth; Miard, Thomas; Chai, Aaron; Marker, Malcolm; Dunbar, Rob; Caldeira, Ken; Lazar, Boaz; Rivlin, Tanya; Mitchell, Brian Gregory; Dove, Sophie; Hoegh-Guldberg, Ove
2015-01-01
Understanding the temporal dynamics of present thermal and pH exposure on coral reefs is crucial for elucidating reef response to future global change. Diel ranges in temperature and carbonate chemistry parameters coupled with seasonal changes in the mean conditions define periods during the year when a reef habitat is exposed to anomalous thermal and/or pH exposure. Anomalous conditions are defined as values that exceed an empirically estimated threshold for each variable. We present a 200-day time series from June through December 2010 of carbonate chemistry and environmental parameters measured on the Heron Island reef flat. These data reveal that aragonite saturation state, pH, and pCO2 were primarily modulated by biologically-driven changes in dissolved organic carbon (DIC) and total alkalinity (TA), rather than salinity and temperature. The largest diel temperature ranges occurred in austral spring, in October (1.5 - 6.6°C) and lowest diel ranges (0.9 - 3.2°C) were observed in July, at the peak of winter. We observed large diel total pH variability, with a maximum range of 7.7 - 8.5 total pH units, with minimum diel average pH values occurring during spring and maximum during fall. As with many other reefs, the nighttime pH minima on the reef flat were far lower than pH values predicted for the open ocean by 2100. DIC and TA both increased from June (end of Fall) to December (end of Spring). Using this high-resolution dataset, we developed exposure metrics of pH and temperature individually for intensity, duration, and severity of low pH and high temperature events, as well as a combined metric. Periods of anomalous temperature and pH exposure were asynchronous on the Heron Island reef flat, which underlines the importance of understanding the dynamics of co-occurrence of multiple stressors on coastal ecosystems.
Kline, David I.; Teneva, Lida; Hauri, Claudine; Schneider, Kenneth; Miard, Thomas; Chai, Aaron; Marker, Malcolm; Dunbar, Rob; Caldeira, Ken; Lazar, Boaz; Rivlin, Tanya; Mitchell, Brian Gregory; Dove, Sophie; Hoegh-Guldberg, Ove
2015-01-01
Understanding the temporal dynamics of present thermal and pH exposure on coral reefs is crucial for elucidating reef response to future global change. Diel ranges in temperature and carbonate chemistry parameters coupled with seasonal changes in the mean conditions define periods during the year when a reef habitat is exposed to anomalous thermal and/or pH exposure. Anomalous conditions are defined as values that exceed an empirically estimated threshold for each variable. We present a 200-day time series from June through December 2010 of carbonate chemistry and environmental parameters measured on the Heron Island reef flat. These data reveal that aragonite saturation state, pH, and pCO2 were primarily modulated by biologically-driven changes in dissolved organic carbon (DIC) and total alkalinity (TA), rather than salinity and temperature. The largest diel temperature ranges occurred in austral spring, in October (1.5 – 6.6°C) and lowest diel ranges (0.9 – 3.2°C) were observed in July, at the peak of winter. We observed large diel total pH variability, with a maximum range of 7.7 – 8.5 total pH units, with minimum diel average pH values occurring during spring and maximum during fall. As with many other reefs, the nighttime pH minima on the reef flat were far lower than pH values predicted for the open ocean by 2100. DIC and TA both increased from June (end of Fall) to December (end of Spring). Using this high-resolution dataset, we developed exposure metrics of pH and temperature individually for intensity, duration, and severity of low pH and high temperature events, as well as a combined metric. Periods of anomalous temperature and pH exposure were asynchronous on the Heron Island reef flat, which underlines the importance of understanding the dynamics of co-occurrence of multiple stressors on coastal ecosystems. PMID:26039687
New cytotoxic and anti-inflammatory compounds isolated from Morus alba L.
Qin, Jing; Fan, Min; He, Juan; Wu, Xing-De; Peng, Li-Yan; Su, Jia; Cheng, Xiao; Li, Yan; Kong, Ling-Mei; Li, Rong-Tao; Zhao, Qin-Shi
2015-01-01
Six Diels-Alder adducts (1-6) and nine prenylated flavanones (7-15) were isolated from the root bark of Morus alba L. Among them, soroceal B (1) and sanggenol Q (7) were new compounds. Their structures were elucidated on the basis of extensive spectroscopic methods, including 1D and 2D NMR techniques. Compounds 1-3, 9, 10, 12, 13 and 15 exhibited cytotoxic activity against five human tumour lines and compound 2 inhibited significantly selective cytotoxic activities towards HL-60 and AGS cells with IC50 of 3.4 and 3.6 μM. Compounds 3, 5, 9 and 12 exhibited moderate inhibitory activity against nitric oxide production in LPS-activated RAW264.7.
Control of femtosecond laser driven retro-Diels-Alder-like reaction of dicyclopentadiene
Das, Dipak Kumar; Goswami, Tapas; Goswami, Debabrata
2013-01-01
Using femtosecond time resolved degenerate pump-probe mass spectrometry coupled with simple linearly chirped frequency modulated pulse, we elucidate that the dynamics of retro-Diels-Alder-like reaction of diclopentadiene (DCPD) to cyclopentadiene (CPD) in supersonic molecular beam occurs in ultrafast time scale. Negatively chirped pulse enhances the ion yield of CPD, as compared to positively chirped pulse. This indicates that by changing the frequency (chirp) of the laser pulse we can control the ion yield of a chemical reaction. PMID:23814449
Sasaki, S; Ishibashi, N; Kuwamura, T; Sano, H; Matoba, M; Nisikawa, T; Maeda, M
1998-11-03
A series of 6,11-ethanobenzo[b]quinolizinium derivatives was synthesized through the Diels-Alder reaction between azoniaanthracne and the corresponding 1,1-disubstituted olefin. After a systematic investigation for achieving rapid synthesis, it was found that the reaction is accelerated in polar media such as H2O and trifluoroethanol. In particular, excellent acceleration was effected by microwave irradiation. The new fluorine-substituted ligands thus obtained exhibited potential affinity toward NMDA receptors.
Castagnolo, Daniele; Botta, Lorenzo; Botta, Maurizio
2009-07-27
An efficient and stereoselective synthesis of D,L-gulose was described. The key step of the synthetic route is represented by a multicomponent enyne cross metathesis-hetero Diels-Alder reaction which allows the formation of the pyran ring from cheap and commercially available substrates in a single synthetic step. The synthesis of D,L-gulose was accomplished without the use of protecting groups making this approach highly desirable also in terms of atom economy.
Van Der Eycken, Erik; Appukkuttan, Prasad; De Borggraeve, Wim; Dehaen, Wim; Dallinger, Doris; Kappe, C Oliver
2002-11-01
Inter- and intramolecular hetero-Diels-Alder reactions in a series of functionalized 2(1H)-pyrazinones were investigated under controlled microwave irradiation. The cycloaddition reactions were efficiently performed in sealed tubes, utilizing either a combination of 1,2-dichloroethane and a thermally stable ionic liquid, or 1,2-dichlorobenzene as reaction medium. In all cases, a significant rate-enhancement using microwave flash heating as compared to thermal heating was observed.
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.
CO2 time series patterns in contrasting headwater streams of North America
Crawford, John T.; Stanley, Emily H.; Dornblaser, Mark M.; Striegl, Robert G.
2017-01-01
We explored the underlying patterns of temporal stream CO2 partial pressure (pCO2) variability using highfrequency sensors in seven disparate headwater streams distributed across the northern hemisphere. We also compared this dataset of [40,000 pCO2 records with other published records from lotic systems. Individual stream sites exhibited relatively distinct pCO2 patterns over time with few consistent traits across sites. Some sites showed strong diel variability, some exhibited increasing pCO2 with increasing discharge, whereas other streams had reduced pCO2 with increasing discharge or no clear response to changes in flow. The only ‘‘universal’’ signature observed in headwater streams was a late summer pCO2 maxima that was likely driven by greatest rates of organic matter respiration due to highest annual temperatures. However, we did not observe this seasonal pattern in a southern hardwood forest site, likely because the region was transitioning from a severe drought. This work clearly illustrates the heterogeneous nature of headwater streams, and highlights the idiosyncratic nature of a non-conservative solute that is jointly influenced by physics, hydrology, and biology. We suggest that future researchers carefully select sensor locations (within and among streams) and provide additional contextual information when attempting to explain pCO2 patterns.
Kock, Alison; Waries, Sarah; O’Riain, M. Justin
2017-01-01
White sharks (Carcharodon carcharias) are apex predators that play an important role in the structure and stability of marine ecosystems. Despite their ecological importance and protected status, white sharks are still subject to lethal control to reduce the risk of shark bites for recreational water users. The Shark Spotters program, pioneered in Cape Town, South Africa, provides a non-lethal alternative for reducing the risk of human-shark conflict. In this study we assessed the efficacy of the Shark Spotters program in reducing overlap between water users and white sharks at two popular beaches in False Bay, South Africa. We investigated seasonal and diel patterns in water use and shark presence at each beach, and thereafter quantified the impact of different shark warnings from shark spotters on water user abundance. We also assessed the impact of a fatal shark incident on patterns of water use. Our results revealed striking diel and seasonal overlap between white sharks and water users at both beaches. Despite this, there was a low rate of shark-human incidents (0.5/annum) which we attribute partly to the success of the Shark Spotters program. Shark spotters use visual (coloured flags) and auditory (siren) cues to inform water users of risk associated with white shark presence in the surf zone. Our results showed that the highest risk category (denoted by a white flag and accompanying siren) caused a significant reduction in water user abundance; however the secondary risk category (denoted by a red flag with no siren) had no significant effect on water users. A fatal shark incident was shown to negatively impact the number of water users present for at least three months following the incident. Our results indicate that the Shark Spotters program effectively reduces spatial overlap between white sharks and water users when the risk of conflict is highest. PMID:28945806
Engelbrecht, Tamlyn; Kock, Alison; Waries, Sarah; O'Riain, M Justin
2017-01-01
White sharks (Carcharodon carcharias) are apex predators that play an important role in the structure and stability of marine ecosystems. Despite their ecological importance and protected status, white sharks are still subject to lethal control to reduce the risk of shark bites for recreational water users. The Shark Spotters program, pioneered in Cape Town, South Africa, provides a non-lethal alternative for reducing the risk of human-shark conflict. In this study we assessed the efficacy of the Shark Spotters program in reducing overlap between water users and white sharks at two popular beaches in False Bay, South Africa. We investigated seasonal and diel patterns in water use and shark presence at each beach, and thereafter quantified the impact of different shark warnings from shark spotters on water user abundance. We also assessed the impact of a fatal shark incident on patterns of water use. Our results revealed striking diel and seasonal overlap between white sharks and water users at both beaches. Despite this, there was a low rate of shark-human incidents (0.5/annum) which we attribute partly to the success of the Shark Spotters program. Shark spotters use visual (coloured flags) and auditory (siren) cues to inform water users of risk associated with white shark presence in the surf zone. Our results showed that the highest risk category (denoted by a white flag and accompanying siren) caused a significant reduction in water user abundance; however the secondary risk category (denoted by a red flag with no siren) had no significant effect on water users. A fatal shark incident was shown to negatively impact the number of water users present for at least three months following the incident. Our results indicate that the Shark Spotters program effectively reduces spatial overlap between white sharks and water users when the risk of conflict is highest.
Lin, Zhi; Liao, Wenhua; Yang, Yuanyuan; Gao, Zhiling; Ma, Wenqi; Wang, Dianwu; Cao, Yufeng; Li, Jianguo; Cai, Zhenjiang
2015-04-01
Accurately quantifying methane (CH4) and nitrous oxide (N2O) emissions from beef operations in China is necessary to evaluate the contribution of beef cattle to greenhouse gas budgets at the national and global level. Methane and N2O emissions from two intensive beef feedlots in the North China Plain, one with a restricted feeding strategy and high manure collection frequency and the other with an ad libitum feeding strategy and low manure collection frequency, were quantified in the fall and spring seasons using an inverse dispersion technique. The diel pattern of CH4 from the beef feedlot with an ad libitum feed strategy (single peak during a day) differed from that under a restricted feeding condition (multiple peaks during a day), but little difference in the diel pattern of N2O emissions between two feeding strategies was observed. The two-season average CH4 emission rates of the two intensive feedlots were 230 and 198gCH4animal(-1)d(-1) and accounted for 6.7% and 6.8% of the gross energy intake, respectively, indicating little impact of the feeding strategy and manure collection frequency on the CH4 conversion factor at the feedlot level. However, the average N2O emission rates (21.2g N2Oanimal(-1)d(-1)) and conversion factor (8.5%) of the feedlot with low manure collection frequency were approximately 131% and 174% greater, respectively, than the feedlot under high frequency conditions, which had a N2O emission rate and conversion factor of 9.2g N2Oanimal(-1)d(-1) and 3.1%, respectively, indicating that increasing manure collection frequency played an important role in reducing N2O emissions from beef feedlots. In addition, comparison indicated that China's beef and dairy cattle in feedlots appeared to have similar CH4 conversion factors. Copyright © 2015 Elsevier Inc. All rights reserved.
Tough, high performance, addition-type thermoplastic polymers
NASA Technical Reports Server (NTRS)
Pater, Ruth H. (Inventor)
1992-01-01
A tough, high performance polyimide is provided by reacting a triple bond conjugated with an aromatic ring in a bisethynyl compound with the active double bond in a compound containing a double bond activated toward the formation of a Diels-Adler type adduct, especially a bismaleimide, a biscitraconimide, or a benzoquinone, or mixtures thereof. Addition curing of this product produces a high linear polymeric structure and heat treating the highly linear polymeric structure produces a thermally stable aromatic addition-type thermoplastic polyimide, which finds utility in the preparation of molding compounds, adhesive compositions, and polymer matrix composites.
Frapper, Gilles; Bachmann, Christian; Gu, Yanlong; Coval De Sousa, Rodolphe; Jérôme, François
2011-01-14
The role of water in a multicomponent domino reaction (MCR) involving styrene, 2,4-pentanedione, and formaldehyde was studied. Whereas anhydrous conditions produced no reaction, the MCR successfully proceeded in the presence of water, affording the targeted dihydropyran derivatives with good yield. The mechanism of this MCR (Knoevenagel hetero Diels-Alder sequence) was studied with and without explicit water molecules using the SMD continuum solvation model in combination with the B3LYP density functional and the 6-311++G** basis set to compute the water and acetone (aprotic organic solvent) solution Gibbs free energies. In the Knoevenagel step, we found that water acted as a proton relay to favor the formation of more flexible six-membered ring transition state structures both in concerted (direct H(2)O elimination) and stepwise (keto-enol tautomerization and dehydration) pathways. The inclusion of a water molecule in our model resulted in a significant decrease (-8.5 kcal mol(-1)ΔG(water)(‡)) of the direct water elimination activation barrier. Owing to the presence of water, all chemical steps involved in the MCR mechanism had activation free energies barriers lower than 39 kcal mol(-1) at 25 °C in aqueous solvent (<21 kcal mol(-1) ZPE corrected electronic energies barriers). Consequently, the MCR proceeded without the assistance of any catalyst.
Determination of Trophic State Changes with Diel Dissolved Oxygen: A Case Study in a Shallow Lake.
Xu, Zhen; Xu, Y Jun
2015-11-01
Current trophic state indices (TSI) have been reported to have limitations in assessing changes in eutrophication status of shallow waters. This study aimed to use intensive measurements on dissolved oxygen (DO) to improve the determination of tropic state changes. The authors deployed an environment monitoring buoy in a eutrophic shallow lake and recorded water temperature, DO, and chlorophyll-a concentrations at 15-minute intervals for two 1-year periods: from August 2008 to July 2009 and from August 2013 to July 2014. In addition, they recorded water levels over the same periods and collected water samples for nutrient analysis. The authors analyzed the high-time resolution DO records, compared the diel DO trends between the two 1-year periods, and proposed a new TSI using DO. They found that analyzing the change in diel DO ranges can improve commonly used methods for classifying trophic states and assessing the change of eutrophication status of waterbodies.
Diel Variations in Optical Properties of Micromonas pusilla, a Prasinophyte
NASA Technical Reports Server (NTRS)
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.
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.
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.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Mestres, J.; Duran, M.; Sola, M.
1996-05-02
The eight unique Diels-Alder cycloadditions of butadiene to C{sub 70} are analyzed theoretically and compared with the well-established, two possible Diels-Alder cycloadditions of butadiene to C{sub 60}. Full geometry optimizations of reactants, adducts, and transition states are performed using the AMI semiempirical method followed by single-point ab initio energy calculations. The results show that the cycloaddition of butadiene to the C{sub 70} fullerene in the gas phase is slightly more reactive than that to C{sub 60}. However, in toluene solution calculations yield that the different solvent effects on C{sub 60} and C{sub 70} cause a significant decrease of the energymore » barrier in the C{sub 60} cycloaddition, thus predicting a larger reactivity for C{sub 60} as compared to the C{sub 70} fullerene. 36 refs., 2 figs., 3 tabs.« less
Seasonal thermal ecology of adult walleye (Sander vitreus) in Lake Huron and Lake Erie.
Peat, Tyler B; Hayden, Todd A; Gutowsky, Lee F G; Vandergoot, Christopher S; Fielder, David G; Madenjian, Charles P; Murchie, Karen J; Dettmers, John M; Krueger, Charles C; Cooke, Steven J
2015-10-01
The purpose of this study was to characterize thermal patterns and generate occupancy models for adult walleye from lakes Erie and Huron with internally implanted biologgers coupled with a telemetry study to assess the effects of sex, fish size, diel periods, and lake. Sex, size, and diel periods had no effect on thermal occupancy of adult walleye in either lake. Thermal occupancy differed between lakes and seasons. Walleye from Lake Erie generally experienced higher temperatures throughout the spring and summer months than did walleye in Lake Huron, due to limnological differences between the lakes. Tagged walleye that remained in Saginaw Bay, Lake Huron (i.e., adjacent to the release location), as opposed to those migrating to the main basin of Lake Huron, experienced higher temperatures, and thus accumulated more thermal units (the amount of temperature units amassed over time) throughout the year. Walleye that migrated toward the southern end of Lake Huron occupied higher temperatures than those that moved toward the north. Consequently, walleye that emigrated from Saginaw Bay experienced thermal environments that were more favorable for growth as they spent more time within their thermal optimas than those that remained in Saginaw Bay. Results presented in this paper provide information on the thermal experience of wild fish in a large lake, and could be used to refine sex- and lake-specific bioenergetics models of walleye in the Great Lakes to enable the testing of ecological hypotheses. Copyright © 2015 Elsevier Ltd. All rights reserved.
NASA Technical Reports Server (NTRS)
Cullen, John J.; Lewis, Marlon R.; Davis, Curtiss O.; Barber, Richard T.
1992-01-01
Macronutrients persist in the surface layer of the equatorial Pacific because the production of phytoplankton is limited; the nature of this limitation has yet to be resolved. Measurements of photosynthesis as a function of irradiance (P-I) provide information on the control of primary productivity, a question of great biogeochemical importance. Accordingly, P-I was measured in the equatorial Pacific along 150 deg W, during February-March 1988. Diel variability of P-I showed a pattern consistent with nocturnal vertical mixing in the upper 20 m followed by diurnal stratification, causing photoinhibition near the surface at midday. Otherwise, the distribution of photosynthetic parameters with depth and the stability of P-I during simulated in situ incubations over 2 days demonstrated that photoadaptation was nearly complete at the time of sampling: photoadaptation had not been effectively countered by upwelling or vertical mixing. Measurements of P-I and chlorophyll during manipulations of trace elements showed that simple precautions to minimize contamination were sufficient to obtain valid rate measurements and that the specific growth rates of phytoplankton were fairly high in situ, a minimum of 0.6/d. Diel variability of beam attenuation also indicated high specific growth rates of phytoplankton and a strong coupling of production with grazing. It appears that grazing is the proximate control on the standing crop of phytoplankton. Nonetheless, the supply of a trace nutrient such as iron might ultimately regulate productivity by influencing species composition and food-web structure.
Seasonal thermal ecology of adult walleye (Sander vitreus) in Lake Huron and Lake Erie
Peat, Tyler B; Hayden, Todd A.; Gutowsky, Lee F G; Vandergoot, Christopher S.; Fielder, David G.; Madenjian, Charles P.; Murchie, Karen J; Dettmers, John M.; Krueger, Charles C.; Cooke, Steven J.
2015-01-01
The purpose of this study was to characterize thermal patterns and generate occupancy models for adult walleye from lakes Erie and Huron with internally implanted biologgers coupled with a telemetry study to assess the effects of sex, fish size, diel periods, and lake. Sex, size, and diel periods had no effect on thermal occupancy of adult walleye in either lake. Thermal occupancy differed between lakes and seasons. Walleye from Lake Erie generally experienced higher temperatures throughout the spring and summer months than did walleye in Lake Huron, due to limnological differences between the lakes. Tagged walleye that remained in Saginaw Bay, Lake Huron (i.e., adjacent to the release location), as opposed to those migrating to the main basin of Lake Huron, experienced higher temperatures, and thus accumulated more thermal units (the amount of temperature units amassed over time) throughout the year. Walleye that migrated toward the southern end of Lake Huron occupied higher temperatures than those that moved toward the north. Consequently, walleye that emigrated from Saginaw Bay experienced thermal environments that were more favorable for growth as they spent more time within their thermal optimas than those that remained in Saginaw Bay. Results presented in this paper provide information on the thermal experience of wild fish in a large lake, and could be used to refine sex- and lake-specific bioenergetics models of walleye in the Great Lakes to enable the testing of ecological hypotheses.
Teuber, Lena; Schukat, Anna; Hagen, Wilhelm; Auel, Holger
2013-01-01
Oxygen minimum zones (OMZs) affect distribution patterns, community structure and metabolic processes of marine organisms. Due to the prominent role of zooplankton, especially copepods, in the marine carbon cycle and the predicted intensification and expansion of OMZs, it is essential to understand the effects of hypoxia on zooplankton distribution and ecophysiology. For this study, calanoid copepods were sampled from different depths (0-1800 m) at eight stations in the eastern tropical Atlantic (3 °47'N to 18 °S) during three expeditions in 2010 and 2011. Their horizontal and vertical distribution was determined and related to the extent and intensity of the OMZ, which increased from north to south with minimum O2 concentrations (12.7 µmol kg(-1)) in the southern Angola Gyre. Calanoid copepod abundance was highest in the northeastern Angola Basin and decreased towards equatorial regions as well as with increasing depth. Maximum copepod biodiversity was observed in the deep waters of the central Angola Basin. Respiration rates and enzyme activities were measured to reveal species-specific physiological adaptations. Enzyme activities of the electron transport system (ETS) and lactate dehydrogenase (LDH) served as proxies for aerobic and anaerobic metabolic activity, respectively. Mass-specific respiration rates and ETS activities decreased with depth of occurrence, consistent with vertical changes in copepod body mass and ambient temperature. Copepods of the families Eucalanidae and Metridinidae dominated within the OMZ. Several of these species showed adaptive characteristics such as lower metabolic rates, additional anaerobic activity and diel vertical migration that enable them to successfully inhabit hypoxic zones.
Teuber, Lena; Schukat, Anna; Hagen, Wilhelm; Auel, Holger
2013-01-01
Oxygen minimum zones (OMZs) affect distribution patterns, community structure and metabolic processes of marine organisms. Due to the prominent role of zooplankton, especially copepods, in the marine carbon cycle and the predicted intensification and expansion of OMZs, it is essential to understand the effects of hypoxia on zooplankton distribution and ecophysiology. For this study, calanoid copepods were sampled from different depths (0–1800 m) at eight stations in the eastern tropical Atlantic (3°47′N to 18°S) during three expeditions in 2010 and 2011. Their horizontal and vertical distribution was determined and related to the extent and intensity of the OMZ, which increased from north to south with minimum O2 concentrations (12.7 µmol kg−1) in the southern Angola Gyre. Calanoid copepod abundance was highest in the northeastern Angola Basin and decreased towards equatorial regions as well as with increasing depth. Maximum copepod biodiversity was observed in the deep waters of the central Angola Basin. Respiration rates and enzyme activities were measured to reveal species-specific physiological adaptations. Enzyme activities of the electron transport system (ETS) and lactate dehydrogenase (LDH) served as proxies for aerobic and anaerobic metabolic activity, respectively. Mass-specific respiration rates and ETS activities decreased with depth of occurrence, consistent with vertical changes in copepod body mass and ambient temperature. Copepods of the families Eucalanidae and Metridinidae dominated within the OMZ. Several of these species showed adaptive characteristics such as lower metabolic rates, additional anaerobic activity and diel vertical migration that enable them to successfully inhabit hypoxic zones. PMID:24223716
Kimball, B.A.; Runkel, R.L.; Walton-Day, K.
2010-01-01
Historical mining has left complex problems in catchments throughout the world. Land managers are faced with making cost-effective plans to remediate mine influences. Remediation plans are facilitated by spatial mass-loading profiles that indicate the locations of metal mass-loading, seasonal changes, and the extent of biogeochemical processes. Field-scale experiments during both low- and high-flow conditions and time-series data over diel cycles illustrate how this can be accomplished. A low-flow experiment provided spatially detailed loading profiles to indicate where loading occurred. For example, SO42 - was principally derived from sources upstream from the study reach, but three principal locations also were important for SO42 - loading within the reach. During high-flow conditions, Lagrangian sampling provided data to interpret seasonal changes and indicated locations where snowmelt runoff flushed metals to the stream. Comparison of metal concentrations between the low- and high-flow experiments indicated substantial increases in metal loading at high flow, but little change in metal concentrations, showing that toxicity at the most downstream sampling site was not substantially greater during snowmelt runoff. During high-flow conditions, a detailed temporal sampling at fixed sites indicated that Zn concentration more than doubled during the diel cycle. Monitoring programs must account for diel variation to provide meaningful results. Mass-loading studies during different flow conditions and detailed time-series over diel cycles provide useful scientific support for stream management decisions.
Sorek, Michal; Schnytzer, Yisrael; Ben-Asher, Hiba Waldman; Caspi, Vered Chalifa; Chen, Chii-Shiarng; Miller, David J; Levy, Oren
2018-05-09
All organisms employ biological clocks to anticipate physical changes in the environment; however, the integration of biological clocks in symbiotic systems has received limited attention. In corals, the interpretation of rhythmic behaviours is complicated by the daily oscillations in tissue oxygen tension resulting from the photosynthetic and respiratory activities of the associated algal endosymbiont Symbiodinium. In order to better understand the integration of biological clocks in cnidarian hosts of Symbiodinium, daily rhythms of behaviour and gene expression were studied in symbiotic and aposymbiotic morphs of the sea-anemone Aiptasia diaphana. The results showed that whereas circatidal (approx. 12-h) cycles of activity and gene expression predominated in aposymbiotic morphs, circadian (approx. 24-h) patterns were the more common in symbiotic morphs, where the expression of a significant number of genes shifted from a 12- to 24-h rhythm. The behavioural experiments on symbiotic A. diaphana displayed diel (24-h) rhythmicity in body and tentacle contraction under the light/dark cycles, whereas aposymbiotic morphs showed approximately 12-h (circatidal) rhythmicity. Reinfection experiments represent an important step in understanding the hierarchy of endogenous clocks in symbiotic associations, where the aposymbiotic Aiptasia morphs returned to a 24-h behavioural rhythm after repopulation with algae. Whilst some modification of host metabolism is to be expected, the extent to which the presence of the algae modified host endogenous behavioural and transcriptional rhythms implies that it is the symbionts that influence the pace. Our results clearly demonstrate the importance of the endosymbiotic algae in determining the timing and the duration of the extension and contraction of the body and tentacles and temporal gene expression.
Sung, Kijune; Lee, Geun-Joo; Munster, Clyde
2015-01-01
Wetland plants are important components that influence the biogeochemistry of wetland ecosystems. Therefore, remediation performance in wetlands can differ depending on the growth forms of plants. In this study, the effects of Eichhornia crassipes (floating plant) and Ceratophyllum demersum (submerged plant) on the wetland soil and water environments were investigated using a microcosm study with simulated hydrology of retention-type wetlands between rainfall events. The C. demersum microcosm (SP) showed the fastest recovery with a diel fluctuation pattern of dissolved oxygen, pH, and oxidation-reduction potential (ORP) from the impacts of nutrient inflow. Moreover, SP exhibited the lowest decrease in sediment ORP, the highest dehydrogenase activity, and more organic forms of nitrogen and phosphorus. E. crassipes microcosms exhibited the lowest water temperature, and efficiently controlled algae. In the presence of plants, the total nitrogen and phosphorus concentrations in water rapidly decreased, and the composition of organic and inorganic nutrient forms was altered along with a decrease in concentration. The results indicate that wetland plants help retain nutrients in the system, but the effects varied based on the wetland plant growth forms.
Wu, Yonghua; Wang, Haifeng; Hadly, Elizabeth A
2017-04-20
Nocturnality is a key evolutionary innovation of mammals that enables mammals to occupy relatively empty nocturnal niches. Invasion of ancestral mammals into nocturnality has long been inferred from the phylogenetic relationships of crown Mammalia, which is primarily nocturnal, and crown Reptilia, which is primarily diurnal, although molecular evidence for this is lacking. Here we used phylogenetic analyses of the vision genes involved in the phototransduction pathway to predict the diel activity patterns of ancestral mammals and reptiles. Our results demonstrated that the common ancestor of the extant Mammalia was dominated by positive selection for dim-light vision, supporting the predominate nocturnality of the ancestral mammals. Further analyses showed that the nocturnality of the ancestral mammals was probably derived from the predominate diurnality of the ancestral amniotes, which featured strong positive selection for bright-light vision. Like the ancestral amniotes, the common ancestor of the extant reptiles and various taxa in Squamata, one of the main competitors of the temporal niches of the ancestral mammals, were found to be predominate diurnality as well. Despite this relatively apparent temporal niche partitioning between ancestral mammals and the relevant reptiles, our results suggested partial overlap of their temporal niches during crepuscular periods.
Dewey, M.R.; Richardson, W.B.; Zigler, S.J.
1997-01-01
We studied the trophic interactions and spatial distributions of bluegills Lepomis macrochirus and largemouth bass Micropterus salmoides in a macrophyte bed in Lake Onalaska, a backwater lake in the upper Mississippi River. The diets of adult and age-0 bluegills were similar and changed seasonally probably in response to changes in life stages of macroinvertebrates (i.e. emergence of winged adults). Diets and diel patterns of abundance of bluegill suggest that age-0 and adults were feeding in the vegetated, littoral zone. Predation by age-0 largemouth bass appears to influence use of vegetated habitat by age-0 bluegills. In summer, when most age-0 bluegills were vulnerable to predation by age-0 largemouth bass, bluegill abundance was strongly correlated with vegetation biomass. In October and November, piscivory by age-0 largemouth bass was limited by gape. Consequently, the relationship between the abundance of age-0 bluegills and vegetation biomass was weakened because predation risk by age-0 largemouth bass was reduced.
Giustiniano, Mariateresa; Mercalli, Valentina; Amato, Jussara; Novellino, Ettore; Tron, Gian Cesare
2015-08-21
An expeditious multicomponent reaction to synthesize tetrasubstituted furo[2,3-d]pyridazin-4(5H)-ones is reported. In brief, hydrazonoyl chlorides react with isocyanoacetamides, in the presence of TEA, to give 1,3-oxazol-2-hydrazones which, without being isolated, can react with dimethylacetylene dicarboxylate to afford furo[2,3-d]pyridazin-4(5H)-ones with an unprecedented level of complexity in a triple domino Diels-Alder/retro-Diels-Alder/lactamization reaction sequence.
Vertical distributions and diel migrations of Euthecosomata in the northwest Sargasso Sea
NASA Astrophysics Data System (ADS)
Wormuth, John H.
1981-12-01
Vertical distributions and seasonal variations in abundance of nine abundant or frequent pteropod species or subspecies in the northwest Sargasso Sea are described. Factor analyses yielded two groups, diel migrators and non-migrators. In terms of water column abundances, tows taken in August and November are similar, as are tows in December and April. Most species show significant within-species agreement in depth distribution over the year but high variability in abundance. Regression analyses using environmental parameters as independent variables show significant correlations of species abundances with temperature.
Ren, Ji-Wei; Wang, Jing; Xiao, Jun-An; Li, Jun; Xiang, Hao-Yue; Chen, Xiao-Qing; Yang, Hua
2017-06-16
Hydrogen-bonding organocatalysts L-pyroglutamic sulphonamides were readily synthesized for the first time by fully exploiting the potentials of L-pyroglutamic acid. The newly designed catalyst was successfully applied in catalyzing asymmetric Diels-Alder cyclization of methyleneindolinones with 2-vinyl-1H-indoles to efficiently assemble carbazolespirooxindoles in excellent stereoselectivity (up to 99% ee, >20:1 dr) and yields (up to 99%). Mechanistic studies disclosed that the well-designed hydrogen-bonding modes between L-pyroglutamic sulphonamide and substrates were crucial for stereocontrol in the cyclization.
Fekete, Beáta; Palkó, Márta; Haukka, Matti; Fülöp, Ferenc
2017-04-13
From 2-aminonorbornene hydroxamic acids, a simple and efficient method for the preparation of pyrrolo[1,2- a ]pyrimidine enantiomers is reported. The synthesis is based on domino ring-closure followed by microwave-induced retro Diels-Alder (RDA) protocols, where the chirality of the desired products is transferred from norbornene derivatives. The stereochemistry of the synthesized compounds was proven by X-ray crystallography. The absolute configuration of the product is determined by the configuration of the starting amino hydroxamic acid.
Rate variations of a hetero-Diels--Alder reaction in supercritical fluid CO{sub 2}
DOE Office of Scientific and Technical Information (OSTI.GOV)
Thompson, R.L.; Glaeser, R.; Bush, D.
1999-11-01
The hetero-Diels-Alder reaction between anthracene and excess 4-phenyl-1,2,4-triazoline-3,5-dione has been investigated in supercritical CO{sub 2} at 40 C and pressures between 75 and 216 bar. Biomolecular reaction rate constants have been measured via fluorescence spectroscopy by following the decrease in anthracene concentration with reaction time. The reaction rate is elevated in the vicinity of the critical pressure. This difference is consistent with local composition enhancement and can be modeled with the Peng-Robinson equation of state.
Diels-Alder reactions of five-membered heterocycles containing one heteroatom
Ding, Xiaoyuan; Nguyen, Son T.; Williams, John D.; Peet, Norton P.
2015-01-01
Diels-Alder reactions of five-membered heterocycles containing one heteroatom with an N-arylmaleimide were studied. Cycloaddition of 2,5-dimethylfuran (4) with 2-(4-methylphenyl)maleimide (3) in toluene at 60 °C gave bicyclic adduct 5. Cycloadditions of 3 with 2,5-dimethylthiophene (11) and 1,2,5-trimethylpyrrole (14) were also studied. Interestingly, the bicyclic compound 5 cleanly rearranged, with loss of water, when treated with p-toluenesulfonic acid in toluene at 80 °C to give 4,7-dimethyl-2-p-tolylisoindoline-1,3-dione (6). PMID:25838605
DOE Office of Scientific and Technical Information (OSTI.GOV)
Steen, Jr, J P; Gunter, G; Hartwig, E O
1982-01-01
In the study 128 copepod species and 43 other zooplankton taxa were identified from four depth strata (0 to 50 m, 50 to 100 m, 100 to 300 m and 300 to 500 m). Duplicate step-oblique tows at six hour intervals over 24 hours were taken at a site in the Gulf of Mexico. The distribution of zooplankton numbers and sizes, and species diversity, richness and evenness through a diel period are described.
Spectacular Rate Enhancement of the Diels-Alder Reaction at the Ionic Liquid/n-Hexane Interface.
Beniwal, Vijay; Manna, Arpan; Kumar, Anil
2016-07-04
The use of the ionic liquid/n-hexane interface as a new class of reaction medium for the Diels-Alder reaction gives large rate enhancements of the order of 10(6) to 10(8) times and high stereoselectivity, as compared to homogeneous media. The rate enhancement is attributed to the H-bonding abilities and polarities of the ionic liquids, whereas the hydrophobicity of ionic liquids was considered to be the factor in controlling stereoselectivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Liu, Cong; Assary, Rajeev S.; Curtiss, Larry A.
2014-06-26
Upgrading of furan and small oxygenates obtained from the decomposition of cellulosic materials via formation of carbon-carbon bonds is critical to effective conversion of biomass to liquid transportation fuels. Simulation-driven molecular level understanding of carbon-carbon bond formation is required to design efficient catalysts and processes. Accurate quantum chemical methods are utilized here to predict the reaction energetics for conversion of furan (C4H4O) to C5-C8 ethers and the transformation of furfural (C5H6O2) to C13-C26 alkanes. Furan, can be coupled with various C1 to C4 lower molecular weight carbohydrates obtained from the pyrolysis via Diels-Alder type reactions in the gas phase tomore » produce C5-C8 cyclic ethers. The computed reaction barriers for these reactions (~25 kcal/mol) are lower than the cellulose activation or decomposition reactions (~50 kcal/mol). Cycloaddition of C5-C8 cyclo-ethers with furans can also occur in the gas phase, and the computed activation energy is similar to that of the first Diels-Alder reaction. Furfural, obtained from biomass, can be coupled with aldehydes or ketones with α-hydrogen atoms to form longer chain aldol products and these aldol products can undergo vapor phase hydrocycloaddition (activation barrier of ~20 kcal/mol) to form the precursors of C26 cyclic hydrocarbons. These thermochemical studies provide the basis for further vapor phase catalytic studies required for upgrading of furans/furfurals to longer chain hydrocarbons.« less
Liu, Ling; Bruhn, Torsten; Guo, Liangdong; Götz, Daniel C G; Brun, Reto; Stich, August; Che, Yongsheng; Bringmann, Gerhard
2011-02-25
Chloropupukeanolides C-E (8-10), three highly functionalized secondary metabolites featuring a novel spiroketal skeleton derived from the chlorinated tricyclo-[4.3.1.0(3, 7)]-decane (pupukeanane) and the 2,6-dihydroxy-4-methylbenzoic acid moieties, were isolated from the scale-up fermentation extract of the plant endophytic fungus Pestalotiopsis fici. The constitutions of compounds 8-10 were elucidated primarily by NMR experiments. Their relative configurations were deduced by analogy to metabolites 4-6, which were previously isolated from the same fungus. The absolute configuration of 8 was assigned by X-ray crystallography and those of 9 and 10 by quantum-chemical CD calculations. Biogenetically, chloropupukeanolides C-E (8-10) are presumably derived from the same oxidation-induced Diels-Alder reaction pathway as compounds 1 and 4-7, via the putative biosynthetic precursors 2 and 3. The opposite configurations of the complete "Southern parts" of 8 and 9 suggests that this Diels-Alder reaction is stereochemically not very selective. Compounds 8-10 showed significant cytotoxicity against a small panel of human tumor cell lines and weak activities against the pathogens of tropical diseases. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
NASA Astrophysics Data System (ADS)
Kiselev, V. D.; Kornilov, D. A.; Anikin, O. V.; Latypova, L. I.; Konovalov, A. I.
2017-03-01
The rate of the reaction between 9,10-anthracenedimethanol and maleic anhydride in 1,4-dioxane, acetonitrile, trichloromethane, and toluene is studied at 25, 35, 45°C in the pressure range of 1-1772 bar. The rate constants, enthalpies, entropies and activation volumes are determined. It is shown that the rate of reaction with 9,10-anthracenedimethanol is approximately one order of magnitude higher than with 9-anthracenemethanol.
Han, Xun; Floreancig, Paul E
2014-10-06
Spiroacetals can be formed through a one-pot sequence of a hetero-Diels-Alder reaction, an oxidative carbon-hydrogen bond cleavage, and an acid treatment. This convergent approach expedites access to a complex molecular subunit which is present in numerous biologically active structures. The utility of the protocol is demonstrated through its application to a brief synthesis of the actin-binding cytotoxin bistramide A. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Movements and diving behavior of internesting green turtles along Pacific Costa Rica.
Blanco, Gabriela S; Morreale, Stephen J; Seminoff, Jeffrey A; Paladino, Frank V; Piedra, Rotney; Spotila, James R
2013-09-01
Using satellite transmitters, we determined the internesting movements, spatial ecology and diving behavior of East Pacific green turtles (Chelonia mydas) nesting on Nombre de Jesús and Zapotillal beaches along the Pacific coast of northwestern Costa Rica. Kernel density analysis indicated that turtles spent most of their time in a particularly small area in the vicinity of the nesting beaches (50% utilization distribution was an area of 3 km(2) ). Minimum daily distance traveled during a 12 day internesting period was 4.6 ± 3.5 km. Dives were short and primarily occupied the upper 10 m of the water column. Turtles spent most of their time resting at the surface and conducting U-dives (ranging from 60 to 81% of the total tracking time involved in those activities). Turtles showed a strong diel pattern, U-dives mainly took place during the day and turtles spent a large amount of time resting at the surface at night. The lack of long-distance movements demonstrated that this area was heavily utilized by turtles during the nesting season and, therefore, was a crucial location for conservation of this highly endangered green turtle population. The unique behavior of these turtles in resting at the surface at night might make them particularly vulnerable to fishing activities near the nesting beaches. © 2012 Wiley Publishing Asia Pty Ltd, ISZS and IOZ/CAS.
Ozone concentrations at a selected high-elevation forest site downwind Mexico City
NASA Astrophysics Data System (ADS)
Torres-JArdon, R.
2013-05-01
Torres-Jardón, R.*, Rosas-Pérez, I., Granada-Macías, L. M., Ruiz-Suárez, L. G. Centro de Ciencias de la Atmósfera, UNAM, México D. F. México * rtorres@unam.mx For many years, the vegetation of forest species such as Abies religiosa in natural parks located in the southwest mountains of Mexico City has attracted much attention since these parks have been experiencing a severe decline of unclear etiology. The high ozone levels in the area and the observed naked eye macroscopic, histological and cytological injuries on these species, strongly suggest an important contribution of tropospheric ozone to this deterioration process. Apart of historical short monitoring campaigns for measuring ozone levels in these mountains, it is known just a little is known about the present exposure levels at which the local vegetation is exposed. A continuous ozone analyzer has been in operation since 2011 at a high-elevation forest site (Parque Nacional Miguel Hidalgo, PNMH; 3110 m above mean sea level) located downwind of Mexico City Metropolitan Area (MCMA), in order to characterize the local ozone diel amplitude and its seasonal trend, as well as the influence of MCMA on the local O3 concentrations. Hourly average ozone data in PNMH shows that in general, the diel of ozone concentrations in the forest site has a statistical significant correlation with the pattern of ozone levels observed in several monitoring sites (smog receptor sites) within the MCMA, although the high elevation O3 levels are relatively lower than those in the urban area (around 2200 m above mean sea level). It is possible that a part of the oxidants in the air masses are removed by sink deposition processes during the air mass transport across the hills. The diel amplitude of ozone concentrations is small in the cold season, increasing as the seasons advance to June. As in the city, the highest ozone concentrations occur in April or May and the lowest levels during the rainy season, which extends from July to September. Episodes of high concentrations occurred mainly during the dry warm months. Most of the year, nocturnal ozone levels were higher than those registered in the urban area due to the PMH altitude. As a great part of the mountain terrain regularly is above the nocturnal mixing layer formed each day on the valley floor, the ozone remanent levels above this layer in the mountains are kept isolated from urban NOx emissions generated at night. An evaluation of the AOT40 indicator shows that the forest zone is under a strong risk due to ozone pollution. A preliminary analysis of several ozone events in the PNMH shows the suppression of the diel peak, suggesting that a stratospheric intrusion of ozone occurs frequently in high-elevation sites surrounding MCMA.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhu, Z.; Espenson, J.H.
1997-04-16
The title compound proves to be an effective and efficient catalyst for the Diels-Alder reaction when the dienophile is an {alpha},{beta}-unsaturated ketone or aldehyde. It is especially effective in water. Equal amounts of any such dienophile and any of six representative dienes (isoprene, 2-methyl-1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, cyclopentadiene, 1,2,3,4,5,-pentamethylcyclopentadiene, and 1,3-cyclohexadiene) were used, along with 1% MTO. The reactions gave usually > 90% isolated yield of the cycloaddition product except for the larger dienophiles. Nearly exclusively, there was formed one product isomer, the same one that usually predominates. The reactions were often run in chloroform (mostly) and in other organic solvents. Amore » select number were carried out in water, where the reactions gave a greater product yield in a considerably shorter time. Water, itself, is known to enhance the rates of Diels-Alder reactions, but MTO exerts an additional accelerating effect. Kinetics studies were carried out to show that the rate is proportional to the catalyst concentration. The products do not inhibit the reaction. The desirability of MTO as a Diels-Alder catalyst stems from a combination of favorable properties: the inertness to air/oxygen, the tolerance for many substrates, the use of an aqueous medium, and the absence of product inhibition. The initial step appears to be the (weak) coordination of the carbonyl oxygen to the electropositive rhenium center. Steric crowding around rhenium inhibits reactions of the larger dienophiles. 26 refs., 3 figs., 4 tabs.« less
Does biofilm contribute to diel cycling of Zn in High Ore Creek, Montana?
Morris, J.M.; Nimick, D.A.; Farag, A.M.; Meyer, J.S.
2005-01-01
Concentrations of metals cycle daily in the water column of some mining-impacted streams in the Rocky Mountains of the western USA. We hypothesized that biofilm in High Ore Creek, Montana, USA, sorbs and releases Zn on a diel cycle, and this uptake-and-release cycle controls the total and dissolved (0.45-??m filtered) Zn concentrations. We collected water samples from three sites (upstream, middle and downstream at 0, 350 and 650 m, respectively) along a 650-m reach of High Ore Creek during a 47-h period in August 2002 and from the upstream and downstream sites during a 24-h period in August 2003; we also collected biofilm samples at these sites. In 2002 and 2003, total and dissolved Zn concentrations did not exhibit a diel cycle at the upstream sampling site, which was ???30 m downstream from a settling pond through which the creek flows. However, total and dissolved Zn concentrations exhibited a diel cycle at the middle and downstream sampling sites, with the highest Zn concentrations occurring at dawn and the lowest Zn concentrations occurring during late afternoon (>2-fold range of concentrations at the downstream site). Based on (1) concentrations of Zn in biofilm at the three sites and (2) results of streamside experiments that demonstrated Zn uptake and release by nai??ve biofilm during the light and dark hours of a photocycle, respectively, we conclude that Zn uptake in photosynthetic biofilms could contribute a large percentage to the cycling of Zn concentrations in the water column in High Ore Creek. ?? Springer 2005.
Nocturnality constrains morphological and functional diversity in the eyes of reef fishes
2011-01-01
Background Ambient light levels are often considered to drive the evolution of eye form and function. Diel activity pattern is the main mechanism controlling the visual environment of teleost reef fish, with day-active (diurnal) fish active in well-illuminated conditions, whereas night-active (nocturnal) fish cope with dim light. Physiological optics predicts several specific evolutionary responses to dim-light vision that should be reflected in visual performance features of the eye. Results We analyzed a large comparative dataset on morphological traits of the eyes in 265 species of teleost reef fish in 43 different families. The eye morphology of nocturnal reef teleosts is characterized by a syndrome that indicates better light sensitivity, including large relative eye size, high optical ratio and large, rounded pupils. Improved dim-light image formation comes at the cost of reduced depth of focus and reduction of potential accommodative lens movement. Diurnal teleost reef fish, released from the stringent functional requirements of dim-light vision have much higher morphological and optical diversity than nocturnal species, with large ranges of optical ratio, depth of focus, and lens accommodation. Conclusions Physical characteristics of the environment are an important factor in the evolution and diversification of the vertebrate eye. Both teleost reef fish and terrestrial amniotes meet the functional requirements of dim-light vision with a similar evolutionary response of morphological and optical modifications. The trade-off between improved dim-light vision and reduced optical diversity may be a key factor in explaining the lower trophic diversity of nocturnal reef teleosts. PMID:22098687
Chen, Ridao; Duan, Ruigang; Wei, Yannan; Zou, Jianhua; Li, Junwei; Liu, Xiaoyue; Wang, Haiyan; Guo, Ying; Li, Qiuhong; Dai, Jungui
2015-12-01
A chemical investigation of callus cultures of Dysosma versipellis led to the isolation of five new flavonol dimers, dysoverines A-E (1-5), together with 12 known compounds (6-17). The structures of new compounds were determined by the extensive spectroscopic data analyses. The biosynthetic pathway of the new compounds was proposed to involve O-methylation, prenylation, and Diels-Alder cycloaddition, which successively occurred in cultured plant cells. Compounds 1-17 exhibited in vitro neuraminidase inhibitory activities with the IC50 values of 31.0-93.9μM. Copyright © 2015 Elsevier B.V. All rights reserved.
Zelová, Hana; Hanáková, Zuzana; Čermáková, Zuzana; Šmejkal, Karel; Dalĺ Acqua, Stefano; Babula, Petr; Cvačka, Josef; Hošek, Jan
2014-06-27
Chromatographic separation of root extracts of Morus alba and M. nigra led to the identification of the 2-arylbenzofurans moracin C (1), mulberrofuran Y (2), and mulberrofuran H (3), and the prenylated flavonoids kuwanon E (4), kuwanon C (5), sanggenon H (6), cudraflavone B (7), and morusinol (8), and the Diels-Alder adducts soroceal (9), and sanggenon E (10). The cytotoxicity and their antiphlogistic activity, determined as the attenuation of the secretion of TNF-α and IL-1β and the inhibition of NF-κB nuclear translocation in LPS-stimulated macrophages, were evaluated for compounds 1-10.
Large scale patterns in vertical distribution and behaviour of mesopelagic scattering layers
Klevjer, T. A.; Irigoien, X.; Røstad, A.; Fraile-Nuez, E.; Benítez-Barrios, V. M.; Kaartvedt., S.
2016-01-01
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. PMID:26813333
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.
Fall field crickets did not acclimate to simulated seasonal changes in temperature.
Niehaus, Amanda C; Wilson, Robbie S; Storm, Jonathan J; Angilletta, Michael J
2012-02-01
In nature, many organisms alter their developmental trajectory in response to environmental variation. However, studies of thermal acclimation have historically involved stable, unrealistic thermal treatments. In our study, we incorporated ecologically relevant treatments to examine the effects of environmental stochasticity on the thermal acclimation of the fall field cricket (Gryllus pennsylvanicus). We raised crickets for 5 weeks at either a constant temperature (25°C) or at one of three thermal regimes mimicking a seasonal decline in temperature (from 25 to 12°C). The latter three treatments differed in their level of thermal stochasticity: crickets experienced either no diel cycle, a predictable diel cycle, or an unpredictable diel cycle. Following these treatments, we measured several traits considered relevant to survival or reproduction, including growth rate, jumping velocity, feeding rate, metabolic rate, and cold tolerance. Contrary to our predictions, the acclimatory responses of crickets were unrelated to the magnitude or type of thermal variation. Furthermore, acclimation of performance was not ubiquitous among traits. We recommend additional studies of acclimation in fluctuating environments to assess the generality of these findings.
Nadeem, Qaisar; Can, Daniel; Shen, Yunjun; Felber, Michael; Mahmood, Zaid; Alberto, Roger
2014-03-28
We describe the syntheses of half-sandwich complexes of the type [(η(5)-Cp(CONH-R))M(CO)3] with M = Re or (99m)Tc. The R group represents different tri-peptides (tpe) which display high binding affinities for oligopeptide transporters PEPT2. The (99m)Tc complexes were prepared directly from [(99m)Tc(OH2)3(CO)3](+) and Diels-Alder dimerized, cyclopentadienyl derivatized peptides in water. This approach corroborates the feasibility of metal-mediated retro Diels-Alder reactions for the preparation of not only small molecules but also peptides carrying a [(η(5)-Cp)(99m)Tc(CO)3] tag. We synthesized the Diels-Alder product [(HCpCONH-tpe)2] from Thiele's acid [(η(5)-HCpCOOH)2] via double peptide coupling. The Re-complexes [(η(5)-CpCONH-tpe)Re(CO)3] were obtained by attaching [(Cp-COOH)Re(CO)3] directly to the N-terminus of peptides as received from SPPS. The authenticity of the (99m)Tc-complexes is confirmed by chromatographic comparison with the corresponding rhenium complexes, fully characterized by spectroscopic techniques.
Fürmeier, Sven; Metzger, Jürgen O
2004-11-10
The coupling of a simple microreactor to an atmospheric pressure ion source, such as electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI), allows the investigation of reactions in solution by mass spectrometry. The tris(p-bromophenyl)aminium hexachloroantimonate (1(*)(+)SbCl(6)(-))-initiated reactions of phenylvinylsulfide (2) and cyclopentadiene (3) and of trans-anethole (5) and isoprene (6) and the dimerization of 1,3-cyclohexadiene (8) to give the respective Diels-Alder products were studied. These preparatively interesting reactions proceed as radical cation chain reactions via the transient radical cations of the respective dienophiles and of the respective Diels-Alder addition products. These radical cations could be detected directly and characterized unambiguously in the reacting solution by ESI-MS-MS. The identity was confirmed by comparison with MS-MS spectra of the authentic radical cations obtained by APCI-MS and by CID experiments of the corresponding molecular ions generated by EI-MS. In addition, substrates and products could be monitored easily in the reacting solution by APCI-MS.