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Radical addition fragmentation chain transfer (RAFT) polymerization of ferrocenyl (meth)acrylates
(2012)
We report on the controlled free radical homopolymerization of 1-ferrocenylethyl acrylate as well as of three new ferrocene bearing monomers, namely 4-ferrocenylbutyl acrylate, 2-ferrocenylamido-2-methylpropyl acrylate, and 4-ferrocenylbutyl methacrylate, by the RAFT technique. For comparison, the latter monomer was polymerized using ATRP, too. The ferrocene containing monomers were found to be less reactive than their analogues free of ferrocene. The reasons for the low polymerizability are not entirely clear. As the addition of free ferrocene to the reaction mixture did not notably affect the polymerizations, sterical hindrance by the bulky ferrocene moiety fixed on the monomers seems to be the most probable explanation. Molar masses found for 1-ferrocenylethyl acrylate did not exceed 10,000 g mol(-1), while for 4-ferrocenylbutyl (meth) acrylate molar masses of 15,000 g mol(-1) could be obtained. With PDIs as low as 1.3 in RAFT polymerization of the monomers, good control over the polymerization was achieved.
Neuromuscular activity of the lower leg is dependent on the task performed, speed of movement and gender. Whether training volume influences neuromuscular activity is not known. The EMG of physically active persons differing in running mileage was analysed to investigate this. 55 volunteers were allocated to a low (LM: < 30 km), intermediate (IM: > 30 km & < 45 km) or high mileage (HM: > 45 km) group according to their weekly running volume. Neuromuscular activity of the lower leg was measured during running (3.33 m.s(-1)). Mean amplitude values for preactivation, weight acceptance and push-off were calculated and normalised to the mean activity of the entire gait cycle. Higher activity in the gastrocnemius group was observed in weight acceptance in LM compared to IM (+30%) and HM (+25%) but lower activity was present in the push-off for LM compared to IM and HM. For the peroneal muscle, differences were present in the push-off where HM showed increased activity compared to IM (+24%) and LM (+60%). The tibial muscle revealed slightly lower activity during preactivation for the high mileage runners. Neuromuscular activity differs during stance between the high and intermediate group compared to low mileage runners. Slight adaptations in neuromuscular activation indicate a more target-oriented activation strategy possibly due to repetitive training in runners with higher weekly mileage.
This paper presents the state of the art in the development of Semantic-Web-enabled software using object-oriented programming languages. Object triple mapping (OTM) is a frequently used method to simplify the development of such software. A case study that is based on interviews with developers of OTM frameworks is presented at the core of this paper. Following the results of the case study, the formalization of OTM is kept separate from optional but desirable extensions of OTM with regard to metadata, schema matching, and integration into the Semantic-Web infrastructure. The material that is presented is expected to not only explain the development of Semantic-Web software by the usage of OTM, but also explain what properties of Semantic-Web software made developers come up with OTM. Understanding the latter will be essential to get nonexpert software developers to use Semantic-Web technologies in their software.
Ex situ cultivation in botanic gardens could be one possibility to preserve plant species diversity and genetic variation. However, old ex situ populations are often sparsely documented. We were able to retrieve three different ex situ populations and their source in situ populations of the endangered plant species Silene otites after 20-36 years of isolation. Furthermore, three additional wild populations were included in the analysis. Population genetic diversity and differentiation were analysed using AFLP markers. Genetic variation in the ex situ populations was lower than the variation found in the in situ populations. Strong differentiation (F-ST = 0.21-0.36) between corresponding in situ and ex situ populations was observed. Bayesian clustering approach also showed a distinct genetic separation between in situ and ex situ populations. The high genetic differentiation and loss of genetic diversity during spatial and temporal isolation in the ex situ populations can be attributable to small population sizes and unconscious selection during cultivation. Therefore, adequate sampling prior to ex situ cultivation and large effective population sizes are important to preserve genetic diversity. Near-natural cultivation allowing for generation overlap and interspecific competition without artificial selection is recommended as being best for the maintenance of the genetic constitution.
Methane flux rates were measured on a loamy sand soil within perennial and annual energy crops in northeast Germany. The study was performed in closed chambers between 2003 and 2005 with four measurements per week. A mixed linear model including the fixed effects of year, rotation period, crop and fertilisation was applied to determine the influence of climatic factors and soil management on the CH4 flux. Soil water content and air temperature were added as co-variables. With the exception of air temperature, all fixed effects and the co-variable soil water content influenced the CH4 flux. The soil of annual crops consumed 6.1 mu g CH4 m(-2) h(-1), significantly more than the soil of perennial crops with 4.3 mu g CH4 m(-2) h(-1). It is suggested that soil water content plays the key role in CH4 flux between pedosphere and atmosphere. In the range of water contents between 5% and 15%, our model describes that a soil water content increase of 1% induces a net emission of 0.375 mu g CH4 m(-2) h(-1). As the soil of the experimental field was well-drained and aerobic, it represented a net sink for CH4 throughout the study period.
The wide knowledge gaps in invasion biology research that exist in the developing world are crucial impediments to the scientific management and global policymaking on biological invasions. In an effort to fill such knowledge gaps, we present here an inventory of the alien flora of India, based on systematic reviews and rigorous analyses of research studies (ca. 190) published over the last 120 years (1890-2010 AD), and updated with field records of the last two decades. Currently, the inventory comprises of 1,599 species, belonging to 842 genera in 161 families, and constitutes 8.5% of the total Indian vascular flora. The three most species-rich families are Asteraceae (134 spp.), Papilionaceae (114 spp.) and Poaceae (106 spp.), and the three largest genera are Eucalyptus (25 spp.), Ipomoea (22 spp.), and Senna (21 spp.). The majority of these species (812) have no report of escaping from cultivation. Of the remaining subset of 787 species, which have either escaped from intentional cultivation, or spread after unintentional introduction, casuals are represented by 57 spp., casual/naturalised by 114 spp., naturalised by 257 spp., naturalised/invasive by 134 spp., and invasive by 225 spp. Biogeographically, more than one-third (35%) of the alien flora in India has its native ranges in South America, followed by Asia (21%), Africa (20%), Europe (11%), Australia (8%), North America (4%); and cryptogenic (1%). The inventory is expected to serve as the scientific baseline on plant invasions in India, with implications for conservation of global biodiversity.
The aromatic peroxygenase (APO; EC 1.11.2.1) from the agraric basidomycete Marasmius rotula (MroAPO) immobilized at the chitosan-capped gold-nanoparticle-modified glassy carbon electrode displayed a pair of redox peaks with a midpoint potential of -278.5 mV vs. AgCl/AgCl (1 M KCl) for the Fe(2+)/Fe(3+) redox couple of the heme-thiolate-containing protein. MroAPO oxidizes aromatic substrates such as aniline, p-aminophenol, hydroquinone, resorcinol, catechol, and paracetamol by means of hydrogen peroxide. The substrate spectrum overlaps with those of cytochrome P450s and plant peroxidases which are relevant in environmental analysis and drug monitoring. In M. rotula peroxygenase-based enzyme electrodes, the signal is generated by the reduction of electrode-active reaction products (e.g., p-benzoquinone and p-quinoneimine) with electro-enzymatic recycling of the analyte. In these enzyme electrodes, the signal reflects the conversion of all substrates thus representing an overall parameter in complex media. The performance of these sensors and their further development are discussed.
Are gastropods, rather than ants, important dispersers of seeds of myrmecochorous forest herbs?
(2012)
Seed dispersal by ants (myrmecochory) is widespread, and seed adaptations to myrmecochory are common, especially in the form of fatty appendices (elaiosomes). In a recent study, slugs were identified as seed dispersers of myrmecochores in a central European beech forest. Here we used 105 beech forest sites to test whether myrmecochore presence and abundance is related to ant or gastropod abundance and whether experimentally exposed seeds are removed by gastropods. Myrmecochorous plant cover was positively related to gastropod abundance but was negatively related to ant abundance. Gastropods were responsible for most seed removal and elaiosome damage, whereas insects (and rodents) played minor roles. These gastropod effects on seeds were independent of region or forest management. We suggest that terrestrial gastropods can generally act as seed dispersers of myrmecochorous plants and even substitute myrmecochory, especially where ants are absent or uncommon.
The synthesis of block copolymers consisting of poly(vinylidene fluoride) (PVDF) and polystyrene (PS) is reported. Firstly, a propargyl-functionalized alkoxyamine initiator (PgOTIPNO) was prepared and subsequently used for the preparation of a propargyl-terminated PS homopolymer of different chain lengths with low dispersities via nitroxide-mediated radical polymerization. A tailored PVDF homopolymer with iodine end groups originating from iodine transfer polymerization was transformed to PVDF with azide end group. Then, alkyne-terminated PS with different molecular weights and azide-terminated PVDF were joined together via copper-catalyzed alkyne-azide coupling. The block copolymers were characterized using H-1-NMR, F-19-NMR, IR, SEC, and DSC.
Random copolymers of 4-vinylbenzyl tri(oxyethylene) and tetra(oxyethylene) ethers, as well as alternating copolymers of 4-vinylbenzyl methoxytetra(oxyethylene) ether and a series of N-substituted maleimides, were synthesised by conventional free radical polymerisation, reversible addition fragmentation chain transfer (RAFT) and atom transfer radical polymerisation (ATRP). Their thermosensitive behaviour in aqueous solution was studied by turbidimetry and dynamic light scattering. Depending on the copolymer composition, a LCST type phase transition was observed in water. The transition temperature of the obtained random as well as alternating copolymers could be varied within a broad temperature window. In the case of the random copolymers, transition temperatures could be easily fine-tuned, as they showed a linear dependence on the copolymer composition, and were additionally modified by the nature of the polymer end-groups. Alternating copolymers were extremely versatile for implementing a broad range of variations of the phase transition temperatures. Further, while alternating copolymers derived from 4-vinylbenzyl methoxytetra(oxyethylene) ether and maleimides with small hydrophobic side chains underwent macroscopic phase separation when dissolved in water and heated above their cloud point, the incorporation of maleimides bearing larger hydrophobic substituents resulted in the formation of mesoglobules above the phase transition temperature, with hydrodynamic diameters of less than 100 nm.
Multi-wavelength, high spatial brightness operation of a phase-locked stripe-array diode laser
(2012)
Stable continuous wave multi-wavelength operation of a stripe-array diode laser with an externalcavity spectral beam combining geometry is presented. In this setup each emitter of the stripe-array is forced to operate at a different wavelength, which leads to a decoupling between the usually phase-locked emitters. With a reflective diffraction grating with a period of 300 lines per mm, 33 equidistant laser lines around a center wavelength of 978 nm were realized, spanning a spectral range of 26 nm. With this novel approach near-diffraction limited emission with a beam quality of M (2) < 1.2 and an output power of 450 mW was achieved. This laser light source can be used for applications requiring low temporal but high spatial coherence.
Multidirectional communicative interactions in social networks can have a profound effect on mate choice behavior. Male Atlantic molly Poecilia mexicana exhibit weaker mating preferences when an audience male is presented. This could be a male strategy to reduce sperm competition risk: interacting more equally with different females may be advantageous because rivals might copy mate choice decisions. In line with this hypothesis, a previous study found males to show a strong audience effect when being observed while exercising mate choice, but not when the rival was presented only before the choice tests. Audience effects on mate choice decisions have been quantified in poeciliid fishes using association preference designs, but it remains unknown if patterns found from measuring association times translate into actual mating behavior. Thus, we created five audience treatments simulating different forms of perceived sperm competition risk and determined focal males' mating preferences by scoring pre-mating (nipping) and mating behavior (gonopodial thrusting). Nipping did not reflect the pattern that was found when association preferences were measured, while a very similar pattern was uncovered in thrusting behavior. The strongest response was observed when the audience could eavesdrop on the focal male's behavior. A reduction in the strength of focal males' preferences was also seen after the rival male had an opportunity to mate with the focal male's preferred mate. In comparison, the reduction of mating preferences in response to an audience was greater when measuring association times than actual mating behavior. While measuring direct sexual interactions between the focal male and both stimulus females not only the male's motivational state is reflected but also females' behavior such as avoidance of male sexual harassment.
We present a minimal conceptual model for the Atlantic meridional overturning circulation which incorporates the advection of salinity and the basic dynamics of the oceanic pycnocline. Four tracer transport processes following Gnanadesikan in Science 283(5410):2077-2079, (1999) allow for a dynamical adjustment of the oceanic pycnocline which defines the vertical extent of a mid-latitudinal box. At the same time the model captures the salt-advection feedback (Stommel in Tellus 13(2):224-230, (1961)). Due to its simplicity the model can be solved analytically in the purely wind- and purely mixing-driven cases. We find the possibility of abrupt transition in response to surface freshwater forcing in both cases even though the circulations are very different in physics and geometry. This analytical approach also provides expressions for the critical freshwater input marking the change in the dynamics of the system. Our analysis shows that including the pycnocline dynamics in a salt-advection model causes a decrease in the freshwater sensitivity of its northern sinking up to a threshold at which the circulation breaks down. Compared to previous studies the model is restricted to the essential ingredients. Still, it exhibits a rich behavior which reaches beyond the scope of this study and might be used as a paradigm for the qualitative behaviour of the Atlantic overturning in the discussion of driving mechanisms.
This study investigates phenomena that have been claimed to be indicative of Specific Language Impairment (SLI) in German, focusing on subject-verb agreement marking. Longitudinal data from fourteen German-speaking children with SLI, seven monolingual and seven Turkish-German successive bilingual children, were examined. We found similar patterns of impairment in the two participant groups. Both the monolingual and the bilingual children with SLI had correct (present vs. preterit) tense marking and produced syntactically complex sentences such as embedded clauses and wh-questions, but were limited in reliably producing correct agreement-marked verb forms. These contrasts indicate that agreement marking is impaired in German-speaking children with SLI, without any necessary concurrent deficits in either the CP-domain or in tense marking. Our results also show that it is possible to identify SLI from an early successive bilingual child's performance in one of her two languages.
The applicability of equilibrium models for humic-bound transport of toxic or radioactive metals is affected by kinetic processes leading to an increasing inertness of metal-humic complexes. The chemical background is not yet understood. It is widely believed that bound metals undergo an in-diffusion process within the humic colloids, changing from weaker to stronger binding sites. This work is focussed on the competition effect of Al(III) on complexation of Tb(III) or Eu(III) as analogues of trivalent actinides. By using ion exchange and spectroscopic methods, their bound fractions were determined for solutions of Al and humic acid that had been pre-equilibrated for different periods of time. Whilst the amount of bound Al remained unchanged, its blocking effect was found to increase over a time frame of 2 days, which corresponds to the kinetics of the increase in complex inertness reported in most pertinent studies. Thus, the derived "diffusion theory'' turned out to be inapplicable, since it cannot explain an increase in competition for the "initial'' sites. A delayed degradation of polynuclear species (as found for Fe) does not occur. Consequently, the temporal changes must be based on structural rearrangements in the vicinity of bound Al, complicating the exchange or access. Time-dependent studies by laser fluorescence spectroscopy (steady-state and time-resolved) yielded evidence of substantial alterations, which were, however, immediately induced and did not show any significant trend on the time scale of interest, suggesting that the stabilisation process is based on comparatively moderate changes.
We generalize the popular ensemble Kalman filter to an ensemble transform filter, in which the prior distribution can take the form of a Gaussian mixture or a Gaussian kernel density estimator. The design of the filter is based on a continuous formulation of the Bayesian filter analysis step. We call the new filter algorithm the ensemble Gaussian-mixture filter (EGMF). The EGMF is implemented for three simple test problems (Brownian dynamics in one dimension, Langevin dynamics in two dimensions and the three-dimensional Lorenz-63 model). It is demonstrated that the EGMF is capable of tracking systems with non-Gaussian uni- and multimodal ensemble distributions.
Nuclear proteins play a central role in regulating gene expression. Their identification is important for understanding how the nuclear repertoire changes over time under different conditions. Nuclear proteins are often underrepresented in proteomic studies due to the frequently low abundance of proteins involved in regulatory processes. So far, only few studies describing the nuclear proteome of plant species have been published. Recently, the genome sequence of the unicellular green alga Chlamydomonas reinhardtii has been obtained and annotated, allowing the development of further detailed studies for this organism. However, a detailed description of its nuclear proteome has not been reported so far. Here, we present an analysis of the nuclear proteome of the sequenced Chlamydomonas strain cc503. Using LC-MS/MS, we identified 672 proteins from nuclei isolates with a maximum 1% peptide spectrum false discovery rate. Besides well-known proteins (e.g. histones), transcription factors and other transcriptional regulators (e.g. tubby and HMG) were identified. The presence of protein motifs in nuclear proteins was investigated by computational tools, and specific over-represented protein motifs were identified. This study provides new insights into the complexity of the nuclear environment and reveals novel putative protein targets for further studies of nuclear mechanisms.
Despite the great agricultural and ecological importance of efficient use of urea-containing nitrogen fertilizers by crops, molecular and physiological identities of urea transport in higher plants have been investigated only in Arabidopsis. We performed short-time urea-influx assays which have identified a low-affinity and high-affinity (Km of 7.55 mu M) transport system for urea-uptake by rice roots (Oryza sativa). A high-affinity urea transporter OsDUR3 from rice was functionally characterized here for the first time among crops. OsDUR3 encodes an integral membrane-protein with 721 amino acid residues and 15 predicted transmembrane domains. Heterologous expression demonstrated that OsDUR3 restored yeast dur3-mutant growth on urea and facilitated urea import with a Km of c. 10 mu M in Xenopus oocytes. Quantitative reverse-transcription polymerase chain reaction (qPCR) analysis revealed upregulation of OsDUR3 in rice roots under nitrogen-deficiency and urea-resupply after nitrogen-starvation. Importantly, overexpression of OsDUR3 complemented the Arabidopsis atdur3-1 mutant, improving growth on low urea and increasing root urea-uptake markedly. Together with its plasma membrane localization detected by green fluorescent protein (GFP)-tagging and with findings that disruption of OsDUR3 by T-DNA reduces rice growth on urea and urea uptake, we suggest that OsDUR3 is an active urea transporter that plays a significant role in effective urea acquisition and utilisation in rice.
4,4-Dimethyl-1-(trifluoromethylsulfonyl)-1,4-azasilinane 1 and 2,2,6,6-tetramethyl-4-(trifluoromethylsulfonyl)-1,4,2,6-oxazadisilinane 2 were studied by variable temperature dynamic 1H, 13C, 19F NMR spectroscopy and theoretical calculations at the DFT (density functional theory) and MP2 (Moller-Plesset 2) levels of theory. Both kinetic (barriers to ring inversion) and thermodynamic data (frozen conformational equilibria) could be obtained for the two compounds. The computations revealed two minima on the potential energy surface for molecules 1 and 2 corresponding to the rotamers with the CF3SO2 group directed inward and outward the ring, the latter being 0.20.4 kcal/mol (for 1) and 1.1 kcal/mol (for 2) more stable than the former. The vibrational calculations at the DFT and MP2 levels of theory give the values of the free energy difference Delta G degrees for the 'inward' reversible arrow 'outward' equilibrium consistent with those determined from the experimentally measured ratio of the rotamers. The structure of crystalline compound 2 was ascertained by X-ray diffraction analysis.
Afyon Zone, which was derived from the Anatolide-Tauride platform during closure of the Neo-Tethys, is made up of pre-Mesozoic basement and unconformably overlying Triassic-Early Tertiary cover series. The Afyon Zone contains widespread metavolcanic rocks, which are dominated by rhyolite, dacite, and trachyandesite. They form a distinct volcanic succession, which is separated from the underlying Silurian-Lower Carboniferous metacarbonates and meta-siliciclastics by a regional unconformity. Trachyandesitic metavolcanics are made up of massive lava flows, pyroclastics and epiclastics, less frequently, domes and dikes, which were developed on a deeply eroded subaerial landmass. U/Pb and Pb/Pb zircon geochronology yielded Lower Triassic (similar to 250 Ma) ages, which are interpreted as extrusion age of trachyandesitic volcanics. Based on the stratigraphic, geochronological, and geochemical data, we suggest that these Lower Triassic magmatic rocks represent an extensional tectonic setting on the northern active margin of the Gondwana, which led to the development of the northern branch of the Neo-Tethys.
The timing and pattern of surface uplift of Miocene marine sediments capping the southern margin of the Central Anatolian Plateau in southern Turkey provide a first-order constraint on possible mechanisms of regional uplift. Nannofossil, ostracod, and planktic foraminifera biostratigraphy of the Basyayla section (Mut-Ermenek Basin) within the Mut and Kfiselerli Formations suggests a Tortonian age for marine sediments unconformably capping basement rocks at 2 km elevation. The identification of biozone MMi 12a (7.81-8.35 Ma) from planktic foraminifera in the upper part of the section provides the tightest constraint on the age, which is further limited to 8.35-8.108 Ma as a result of the reverse polarity of the collected samples (chron 4r.1 r or 4r.2r). This provides a limiting age for the onset of surface uplift at the margin of one of the world's major orogenic plateaus, from which an average uplift rate of 0.24-0.25 mm/yr can be calculated.
Subhorizontal beds of the uppermost marine sediments exposed throughout the Mut-Ermenek Basin suggest minimal localized deformation, with just minor faulting at the basin margin and broad antiformal deformation across the basin. This implies that the post-8 Ma uplift mechanism must be rooted deep within the crust or in the upper mantle. Published Pn-wave velocity data for the region are compatible with topography compensated by asthenosphere across the southern margin of the plateau, showing a close match to the highest topography when elevations are filtered with a 100-km-wide smoothing window. Uplift along the southern margin of the Central Anatolian Plateau is also reflected by the pattern of Miocene marine sediments capping the margin, which form an asymmetric drape fold over the topography. These observations, together with tomographic evidence for slab steepening and break-off beneath the Eastern Anatolian Plateau, suggest that at least some of the 2 km of post-8 Ma uplift of the southern Central Anatolian Plateau margin is compensated by low-density asthenospheric mantle that upwelled following slab break-off.
Sedimentological, provenance, and detrital thermochronological results for basin fill at the modern deformation front of the northern Andes (6 degrees N latitude) provide a long-term, Eocene to Pliocene record of foreland-basin sedimentation along the Eastern Cordillera !Janos basin boundary in Colombia. Lithofacies assemblages and paleocurrent orientations in the upward-coarsening, 5-km-thick succession of the Nunchia syncline reveal a systematic shift from craton-derived, shallow-marine distal foreland (back-bulge) accumulation in the Mirador Formation, to orogen-sourced, deltaic, and coastalinfluenced sedimentation of the distal to medial foreland (foredeep) in the Carbonera and Leon Formations, to anastomosing fluvial and distributive braided fluvial megafan systems of the proximal foreland (foredeep to wedge-top) basin in the lower and upper Guayabo Formation. These changes in depositional processes and sediment dispersal are supported by up-section variations in detrital zircon U-Pb and (U-Th)/He ages that record exhumation of evolving, compartmentalized sediment source areas in the Eastern Cordillera. The data are interpreted in terms of a progressive eastward advance in foldand-thrust deformation, with late Eocene Oligocene deformation in the axial zone of the Eastern Cordillera along the western edge of Floresta basin (Soapaga thrust), early Miocene reactivation (inversion) of the eastern margin of the Mesozoic rift system (Pajarito and Guaicaramo thrusts), and middle late Miocene propagation of a footwall shortcut fault (Vopal thrust) that created the Nunchia syncline in a wedge-top (piggyback) setting of the eastern foothills along the transition from the Eastern Cordillera to Harms foreland basin. Collectively, the data presented here for the frontal Eastern Cordillera define a general in-sequence pattern of eastwardadvancing fold-and-thrust deformation during Cenozoic east-west shortening in the Colombian Andes.
Discontinuity surfaces are widely recognized but often poorly understood features of epeiric carbonate settings. In sedimentary systems, these features often represent hiatus surfaces below biostratigraphic resolution and may represent a considerable portion of the time contained in the sediment record. From an applied perspective, discontinuities may represent horizontal flow barriers and result in reservoir compartmentalization. Here, a total of 80 condensed surfaces (S1), firmgrounds (S2) and hardgrounds (S3) from a Jurassic (Middle and Upper Bajocian Assoul Formation) ramp setting of the High Atlas in Morocco are carefully documented with respect to their morphology, their secondary impregnation by Fe and Mn oxides and phosphates and their palaeoecological record. A statistical frequency distribution of two surfaces of the S1 type, 1.1 surfaces of the S2 type and 0.4 surfaces of the S3 type per 10 section metres is observed along a 220 m long carbonate succession. Based on two stratigraphically and spatially separated study windows and correlative sections, the stratigraphic frequency distribution, the lateral extent and the nature of facies change across discontinuities are documented in a quantitative manner. Specific features of the study site include the considerable stratigraphic thickness of the Assoul Formation and the conspicuous absence of subaerial-exposure-related features. Based on the data presented here, firmground and hardground surfaces are best interpreted as maximum-regression-related features. Relative sea-level lowstand results in a lowered wave base, and wave orbitals and currents result in sea floor omission and lithification. Care must be taken to avoid overly simplistic interpretations, as differences in bathymetry and carbonate facies result in marked changes in discontinuity characteristics in proximal-distal transects. The data shown here are of significance for those concerned with the interpretation of shoal water carbonate environments and are instrumental in the building of more realistic carbonate reservoir flow models.
Current models of eye movement control are derived from theories assuming serial processing of single items or from theories based on parallel processing of multiple items at a time. This issue has persisted because most investigated paradigms generated data compatible with both serial and parallel models. Here, we study eye movements in a sequential scanning task, where stimulus n indicates the position of the next stimulus n + 1. We investigate whether eye movements are controlled by sequential attention shifts when the task requires serial order of processing. Our measures of distributed processing in the form of parafoveal-on-foveal effects, long-range modulations of target selection, and skipping saccades provide evidence against models strictly based on serial attention shifts. We conclude that our results lend support to parallel processing as a strategy for eye movement control.
Projected scenarios of climate change involve general predictions about the likely changes to the magnitude and frequency of landslides, particularly as a consequence of altered precipitation and temperature regimes. Whether such landslide response to contemporary or past climate change may be captured in differing scaling statistics of landslide size distributions and the erosion rates derived thereof remains debated. We test this notion with simple Monte Carlo and bootstrap simulations of statistical models commonly used to characterize empirical landslide size distributions. Our results show that significant changes to total volumes contained in such inventories may be masked by statistically indistinguishable scaling parameters, critically depending on, among others, the size of the largest of landslides recorded. Conversely, comparable model parameter values may obscure significant, i.e. more than twofold, changes to landslide occurrence, and thus inferred rates of hillslope denudation and sediment delivery to drainage networks. A time series of some of Earth's largest mass movements reveals clustering near and partly before the last glacial-interglacial transition and a distinct step-over from white noise to temporal clustering around this period. However, elucidating whether this is a distinct signal of first-order climate-change impact on slope stability or simply coincides with a transition from short-term statistical noise to long-term steady-state conditions remains an important research challenge.
Climate change, manifested by an increase in mean, minimum, and maximum temperatures and by more intense rainstorms, is becoming more evident in many regions. An important consequence of these changes may be an increase in landslides in high mountains. More research, however, is necessary to detect changes in landslide magnitude and frequency related to contemporary climate, particularly in alpine regions hosting glaciers, permafrost, and snow. These regions not only are sensitive to changes in both temperature and precipitation, but are also areas in which landslides are ubiquitous even under a stable climate. We analyze a series of catastrophic slope failures that occurred in the mountains of Europe, the Americas, and the Caucasus since the end of the 1990s. We distinguish between rock and ice avalanches, debris flows from de-glaciated areas, and landslides that involve dynamic interactions with glacial and river processes. Analysis of these events indicates several important controls on slope stability in high mountains, including: the non-linear response of firn and ice to warming; three-dimensional warming of subsurface bedrock and its relation to site geology; de-glaciation accompanied by exposure of new sediment; and combined short-term effects of precipitation and temperature. Based on several case studies, we propose that the following mechanisms can significantly alter landslide magnitude and frequency, and thus hazard, under warming conditions: (1) positive feedbacks acting on mass movement processes that after an initial climatic stimulus may evolve independently of climate change; (2) threshold behavior and tipping points in geomorphic systems; (3) storage of sediment and ice involving important lag-time effects.
Based on the nucleus-independent chemical shift (NICS) concept, isotropic magnetic shielding values have been computed along the three Cartesian axes for ethene, cyclobutadiene, benzene, naphthalene, and benzocyclobutadiene, starting from the molecular/ring center up to 10 angstrom away. These through-space NMR spectroscopic shielding (TSNMRS) values, which reflect the anisotropic effects, have been broken down into contributions from localized- and canonical molecular orbitals (LMOs and CMOs); these contributions revealed that the proton NMR spectroscopic chemical shifts of nuclei that are spatially close to the C?C double bond or the aromatic ring should not be explained in terms of the conventionally accepted p-electron shielding/deshielding effects. In fact, these effects followed the predictions only for the antiaromatic cyclobutadiene ring.
To investigate how preschoolers acquire a tool use strategy and how they adapt their tool use to a changed situation, 2- to 4-year-olds were asked to retrieve chips from a transparent box with a rod, either by stabbing and lifting through a top opening or by pushing through a front and a back opening. In both conditions, about 40% of the children acquired effective tool use by individual learning, and 90% of the other children learned this by observing only one demonstration. When confronted with a changed situation (i.e., previous opening covered, alternative opening uncovered), children perseverated with the recently learned, but now ineffective tool use strategy. Neither age nor acquisition type of the first strategy affected preschoolers' perseverations. Results indicate that prior tool use experiences have differential effects in situations that require either transferring known functions to novel objects or using a familiar tool for an alternative purpose.
In this study we used molecular markers to screen for the occurrence and prevalence of the three most common haemosporidian genera (Haemoproteus, Plasmodium, and Leucocytozoon) in blood samples of the Philippine Bulbul (Hypsipetes philippinus), a thrush-size passerine bird endemic to the Philippine Archipelago. We then used molecular data to ask whether the phylogeographic patterns in this insular host-parasite system might follow similar evolutionary trajectories or not. We took advantage of a previous study describing the pattern of genetic structuring in the Philippine Bulbul across the Central Philippine Archipelago (6 islands, 7 populations and 58 individuals; three mitochondrial DNA genes). The very same birds were here screened for the occurrence of parasites by species-specific PCR assays of the mitochondrial cytochrome b gene (471 base pairs). Twenty-eight out of the 58 analysed birds had Haemoproteus (48%) infections while just 2% of the birds were infected with either Leucocytozoon or Plasmodium. Sixteen of the 28 birds carrying Haemoproteus had multiple infections. The phylogeography of the Philippine Bulbul mostly reflects the geographical origin of samples and it is consistent with the occurrence of two different subspecies on (1) Semirara and (2) Carabao, Boracay, North Gigante, Panay, and Negros, respectively. Haemoproteus phylogeography shows very little geographical structure, suggesting extensive gene flow among locations. While movements of birds among islands seem very sporadic, we found co-occurring evolutionary divergent parasite lineages. We conclude that historical processes have played a major role in shaping the host phylogeography, while they have left no signature in that of the parasites. Here ongoing population processes, possibly multiple reinvasions mediated by other hosts, are predominant.
The present cross-sectional anthropometric study evaluates new approaches in preventing overweight in children. Anthropometric data were obtained in 289 German children (146 boys, 143 girls) aged 6-11 years and 41 20-29 year old German female students for describing the type of body shape by Metric-Index (thoracic breadth, thoracic depth, height). The data were correlated with 15 fat layers measured with a lipometer with Principal Component Analyses and ANOVA. In females the android respectively gynoid type of body shape was significantly associated with the pyknomorphic respectively leptomorphic type. The study demonstrates that this pattern is established by an age of 8 years, when the earliest maturing children start to enter puberty. This pattern can be used to check the individual's risk of overweight and to recommend preventive healthcare interventions.
While food deprivation has known effects on sympathovagal balance, little is known about hunger's influence on the perception of pain. Since autonomic activities influence many cognitive and emotional processes, this suggests that food deprivation should interact with the perception of pain. This study analyzed the possible effects of short-term food deprivation on pain sensitivity in healthy female participants. This study was comprised of 32 healthy female participants who underwent a 48-hr inpatient hospital investigation. Prior to testing, heart rate and heart rate variability were assessed. After a standardized breakfast, day 1 measurements were taken. Food intake was then not allowed again until the following evening for 22 participants (experimental group), while 12 participants were served standard meals (control group). Pain threshold and tolerance were assessed at 10:00 a. m. on both days using a pressure algometer. Additionally pain experience was examined. Food deprivation significantly reduced pain thresholds and tolerance scores in the experimental group. Additionally, the sympathovagal balance changed, characterized by a decrease in parasympathetic activation. Higher vagal withdrawal after food deprivation was associated with higher pain sensitivity in the experimental group. Furthermore, perceived unpleasantness and pain intensity increased for threshold and tolerance stimuli in the experimental group. We conclude that short-term food deprivation sensitized pain perception in healthy females. An imbalance in sympathovagal activation evoked by food deprivation accounted for this effect. Our results might be a pathogenic mechanism for the development of emotional difficulties associated with disturbed eating behavior.
Macromolecular crowding in living biological cells effects subdiffusion of larger biomolecules such as proteins and enzymes. Mimicking this subdiffusion in terms of random walks on a critical percolation cluster, we here present a case study of EcoRV restriction enzymes involved in vital cellular defence. We show that due to its so far elusive propensity to an inactive state the enzyme avoids non-specific binding and remains well-distributed in the bulk cytoplasm of the cell. Despite the reduced volume exploration capability of subdiffusion processes, this mechanism guarantees a high efficiency of the enzyme. By variation of the non-specific binding constant and the bond occupation probability on the percolation network, we demonstrate that reduced nonspecific binding are beneficial for efficient subdiffusive enzyme activity even in relatively small bacteria cells. Our results corroborate a more local picture of cellular regulation.
During life bones constantly adapt their structure to their mechanical environment via a mechanically controlled process called bone remodeling. For trabecular bone, this process modifies the thickness of each trabecula leading occasionally to full resorption. We describe the irreversible dynamics of the trabecular thickness distribution (TTD) by means of a Markov chain discrete in space and time. By using thickness data from adult patients, we derive the transition probabilities in the chain. This allows a quantification, in terms of geometrical quantities, of the control of bone remodeling and thus to determine the evolution of the TTD with age.
We report the synthesis of free 1,6,7,12-tetraazaperylene (tape). Tape was obtained from 1,1'-bis-2,7-naphthyridine by potassium promoted cyclization followed by oxidation with air. Mono-and dinuclear ruthenium(II) 1,6,7,12-tetraazaperylene complexes of the general formulas [Ru(L-L)(2)(tape)](PF6)(2), [1] (PF6)(2)-[5](PF6)(2), and [{Ru(L-L)(2)}(2)(mu-tape)](PF6)(4), [6](PF6)(4)-[10](PF6)(4), with{L-L = phen, bpy, dmbpy (4,4'-dimethyl-2,2'-bipyridine), dtbbpy (4,4'-ditertbutyl-2,2'-bipyridine) and tmbpy (4,4' 5,5'-tetramethyl-2,2'- bipyridine)}, respectively, were synthesized. The X-ray structures of tape center dot 2CHCl(3) and the mononuclear complexes [Ru(bpy)(2)(tape)](PF6)(2)center dot 0.5CH(3)CN center dot 0.5toluene, [Ru(dmbpy)(2)(tape)] (PF6)(2)center dot 2toluene and [Ru(dtbbpy)(2)(tape)](PF6)(2) center dot 3acetone center dot 0.5H(2)O were solved. The UV-vis absorption spectra and the electrochemical behavior of the ruthenium(II) tape complexes were explored and compared with the data of the analogous dibenzoeilatin (dbneil), 2,2'-bipyrimidine (bpym) and tetrapyrido [3,2-a:2',3'-c:3 '',2''-h:2''',3'''-j] phenazin (tpphz) species.
Background: The goal was to study lipid profiles (TG, TC, LDL, HDL), effects on serum leptin, and fat tissue adiponectin, and resistin as well as body weight effects of Shan He Jian Fei Granules (SHJFG) in rats on a high fat diet.
Methods: Rats were randomly divided into five groups: normal control group fed with normal fat diet, rats on high fat diet receiving low dosage, middle dosage, high dosage of Shan He Jian Fei Granules (SHJFG) as well as a high fat diet group receiving placebo. Rats were treated for 8 weeks. Body weight and naso-anal length of each rat were recorded and Lee's index was calculated. Serum TG, TC, LDL, HDL and leptin concentrations were analyzed. The gene expressions of adiponectin and resistin in adipose tissues were tested by RT-PCR.
Results: Compared to the high-fat diet group, body weights, Lee's indexes, weight of fat tissues and serum TG, TC, LDL and leptin of SHJFG groups significantly decreased (p<0.05), whereas mRNA expressions of adiponectin and resistin of SHJFG groups significantly increased (p<0.05).
Conclusions: SHJFG could significantly lower body weight and serum TG, TC, and LDL of obese rats. The effects of SHJFG in lowering leptin synthesis and raising mRNA expression of adiponectin and resistin in fat tissues may act as part of the mechanisms in lowering body weight of obese rats. Further studies are needed to demonstrate whether SHJFG may also reduce overall cardiovascular morbidity and mortality like other lipid lowering drugs.
The minima on the potential energy surface of 1,2-bis(o-carboxyphenoxy)ethane (CPE) molecule in its electronic ground state were searched by a molecular dynamics simulation performed with MM2 force field. For each of the found minimum-energy conformers, the corresponding equilibrium geometry, charge distribution, HOMO-LUMO energy gap, force field, vibrational normal modes and associated IR and Raman spectral data were determined by means of the density functional theory (DFT) based electronic structure calculations carried out by using B3LYP method and various Pople-style basis sets. The obtained theoretical data confirmed the significant effects of the intra- and inter-molecular hydrogen bonding interactions on the conformational structure, force field, and group vibrations of the molecule. The same data have also revealed that two of the determined stable conformers, both of which exhibit pseudo-crown structure, are considerably more favorable in energy to the others and accordingly provide the major contribution to the experimental spectra of CPE. In the light of the improved vibrational spectral data obtained within the "SQM FF" methodology and "Dual Scale Factors" approach for the monomer and dimer forms of these two conformers, a reliable assignment of the fundamental bands observed in the experimental room-temperature IR and Raman spectra of the molecule was given, and the sensitivities of its group vibrations to conformation, substitution and dimerization were discussed.
In mobile telecommunication networks the trend for an increasing heterogeneity of access networks, the convergence with fixed networks as well as with the Internet are apparent. The resulting future converged network with an expected wide variety of services and a possibly stiff competition between the different market participants as well as legal issues will bring about requirements for charging systems that demand for more flexibility, scalability and efficiency than is available in today's systems. This article surveys recent developments in charging and billing architectures comprising both standardisation work as well as research projects. The second main contribution of this article is a comparison of key features of these developments thus giving a list of essential charging and billing ingredients for tomorrow's communication and service environments.
Metamorphic studies in the cover sequences of the Bitlis complex allow the thermal evolution of the massif to be constrained using metamorphic index minerals. Regionally distributed metamorphic index minerals such as glaucophane, carpholite, relics of carpholite in chloritoid-bearing schists and pseudomorphs after aragonite in marbles record a LT-HP evolution:This demonstrates that the Bitlis complex was subducted and stacked to form a nappe complex during the closure of the Neo-Tethys. During late Cretaceous to Cenozoic evolution the Bitlis complex experienced peak metamorphism of 1.0-1.1 GPa at 350-400 degrees C. During the retrograde evolution temperatures remained below 460 degrees C. Ar-39/Ar-40 dating of white mica in different parageneses from the Bitlis complex reveals a 74-79 Ma (Campanian) date of peak metamorphism and rapid exhumation to an almost isothermal greenschist stage at 67-70 Ma (Maastrichtian). The HP Eocene flysch escaped the greenschist facies stage and were exhumed under very cold conditions. These single stage evolutions contrast with the multistage evolution reported further north from the Amassia-Stepanavan Suture in Armenia. Petrological investigations and isotopic dating show that the collision of Arabia with Eurasia resulted in an assemblage of different blocks derived from the northern as well as from the southern plate and a set of subduction zones producing HP rocks with diverse exhumation histories.
C-branched carbohydrates are of current interest for glycochemistry, are widely found in nature and serve as important subunits in many antibiotics, bacterial polysaccharides and macrolides. Among C-functionalized saccharides, 2-C-branched carbohydrates represent challenging structures for synthetic chemists, since in contrast to C-glycosides they are not easily accessible from glycosyl bromides or other simple precursors. In this perspective we want to summarize recent approaches to 2-C-branched carbohydrates over the past fifteen years. The two main strategies are based on ring-opening of 1,2-cyclopropanated carbohydrates by various reagents, as well as radical additions to glycals and further transformations, developed in our group. Both methods are characterized by high stereoselectivities and good yields and give access to a broad variety of functionalized carbohydrate 2-C-analogs.
Recent observations and modeling studies emphasize the crucial role of fracture mechanics for the stability of ice shelves and thereby the evolution of ice sheets. Here we introduce a macroscopic fracture-density field into a prognostic continuum ice-flow model and compute its evolution incorporating the initiation and growth of fractures as well as their advection with two-dimensional ice flow. To a first approximation, fracture growth is assumed to depend on the spreading rate only, while fracture initiation is defined in terms of principal stresses. The inferred fracture-density fields compare well with observed elongate surface structures. Since crevasses and other deep-reaching fracture structures have been shown to influence the overall ice-shelf dynamics, we propose the fracture-density field introduced here be used as a measure for ice softening and decoupling of the ice flow in fracture-weakened zones. This may yield more accurate and realistic velocity patterns in prognostic simulations. Additionally, the memory of past fracture events links the calving front to the upstream dynamics. Thus the fracture-density field proposed here may be employed in fracture-based calving parameterizations. The aim of this study is to introduce the field and investigate which of the observed surface structures can be reproduced by the simplest physically motivated fracture source terms.
We investigated EEG-power and EEG-coherence changes in a unimodal and a crossmodal matching-to-sample working memory task with either visual or kinesthetic stimuli. Angle-shaped trajectories were used as stimuli presented either as a moving dot on a screen or as a passive movement of a haptic device. Effects were evaluated during the different phases of encoding, maintenance, and recognition. Alpha power was modulated during encoding by the stimulus modality, and in crossmodal conditions during encoding and maintenance by the expected modality of the upcoming test stimulus. These power modulations were observed over modality-specific cortex regions. Systematic changes of coherence for crossmodal compared to unimodal tasks were not observed during encoding and maintenance but only during recognition. There, coherence in the theta-band increased between electrode sites over left central and occipital cortex areas in the crossmodal compared to the unimodal conditions. The results underline the importance of modality-specific representations and processes in unimodal and crossmodal working memory tasks. Crossmodal recognition of visually and kinesthetically presented object features seems to be related to a direct interaction of somatosensory/motor and visual cortex regions by means of long-range synchronization in the theta-band and such interactions seem to take place at the beginning of the recognition phase, i.e. when crossmodal transfer is actually necessary.
Thawing of permafrost and the associated release of carbon constitutes a positive feedback in the climate system, elevating the effect of anthropogenic GHG emissions on global-mean temperatures. Multiple factors have hindered the quantification of this feedback, which was not included in climate carbon-cycle models which participated in recent model intercomparisons (such as the Coupled Carbon Cycle Climate Model Intercomparison Project - (CMIP)-M-4). There are considerable uncertainties in the rate and extent of permafrost thaw, the hydrological and vegetation response to permafrost thaw, the decomposition timescales of freshly thawed organic material, the proportion of soil carbon that might be emitted as carbon dioxide via aerobic decomposition or as methane via anaerobic decomposition, and in the magnitude of the high latitude amplification of global warming that will drive permafrost degradation. Additionally, there are extensive and poorly characterized regional heterogeneities in soil properties, carbon content, and hydrology. Here, we couple a new permafrost module to a reduced complexity carbon-cycle climate model, which allows us to perform a large ensemble of simulations. The ensemble is designed to span the uncertainties listed above and thereby the results provide an estimate of the potential strength of the feedback from newly thawed permafrost carbon. For the high CO2 concentration scenario (RCP8.5), 33-114 GtC (giga tons of Carbon) are released by 2100 (68% uncertainty range). This leads to an additional warming of 0.04-0.23 degrees C. Though projected 21st century permafrost carbon emissions are relatively modest, ongoing permafrost thaw and slow but steady soil carbon decomposition means that, by 2300, about half of the potentially vulnerable permafrost carbon stock in the upper 3 m of soil layer (600-1000 GtC) could be released as CO2, with an extra 1-4% being released as methane. Our results also suggest that mitigation action in line with the lower scenario RCP3-PD could contain Arctic temperature increase sufficiently that thawing of the permafrost area is limited to 9-23% and the permafrost-carbon induced temperature increase does not exceed 0.04-0.16 degrees C by 2300.
Organic geochemical proxy data from surface sediment samples and a sediment core from Lake Donggi Cona were used to infer environmental changes on the northeastern Tibetan Plateau spanning the last 18.4 kyr. Long-chain n-alkanes dominate the aliphatic hydrocarbon fraction of the sediment extract from most surface sediment samples and the sediment core. Unsaturated mid-chain n-alkanes (nC(23:1) and nC(25:1)) have high abundances in some samples, especially in core samples from the late glacial and early Holocene. TOC contents, organic biomarker and non-pollen-palynomorph concentrations and results from organic petrologic analysis on selected samples suggest three major episodes in the history of Lake Donggi Cona. Before ca. 12.6 cal ka BP samples contain low amounts of organic matter due to cold and arid conditions during the late glacial. After 12.6 cal ka BP, relatively high contents of TOC and concentrations of Botryococcus fossils, as well as enhanced concentrations of mid-chain n-alkanes and n-alkenes suggest a higher primary and macrophyte productivity than at present This is supported by high contents of palynomorphs derived from higher plants and algae and was possibly triggered by a decrease of salinity and amelioration of climate during the early Holocene. Since 6.8 cal ka BP Lake Donggi Cona has been an oligotrophic freshwater lake. Proxy data suggest that variations in insolation drive ecological changes in the lake, with increased aquatic productivity during the early Holocene summer insolation maximum. Short-term drops of TOC contents or biomarker concentrations (at 9.9 cal ka BP, after 8.0 and between 3.5 and 1.7 cal ka BP) can possibly be related to relatively cool and dry episodes reported from other sites on the north-eastern Tibetan Plateau, which are hypothesized to occur in phase with Northern Hemisphere cooling events.
The levels of cellular organization, from gene transcription to translation to protein-protein interaction and metabolism, operate via tightly regulated mutual interactions, facilitating organismal adaptability and various stress responses. Characterizing the mutual interactions between genes, transcription factors, and proteins involved in signaling, termed crosstalk, is therefore crucial for understanding and controlling cells' functionality. We aim at using high-throughput transcriptomics data to discover previously unknown links between signaling networks. We propose and analyze a novel method for crosstalk identification which relies on transcriptomics data and overcomes the lack of complete information for signaling pathways in Arabidopsis thaliana. Our method first employs a network-based transformation of the results from the statistical analysis of differential gene expression in given groups of experiments under different signal-inducing conditions. The stationary distribution of a random walk (similar to the PageRank algorithm) on the constructed network is then used to determine the putative transcripts interrelating different signaling pathways. With the help of the proposed method, we analyze a transcriptomics data set including experiments from four different stresses/signals: nitrate, sulfur, iron, and hormones. We identified promising gene candidates, downstream of the transcription factors (TFs), associated to signaling crosstalk, which were validated through literature mining. In addition, we conduct a comparative analysis with the only other available method in this field which used a biclustering-based approach. Surprisingly, the biclustering-based approach fails to robustly identify any candidate genes involved in the crosstalk of the analyzed signals. We demonstrate that our proposed method is more robust in identifying gene candidates involved downstream of the signaling crosstalk for species for which large transcriptomics data sets, normalized with the same techniques, are available. Moreover, unlike approaches based on biclustering, our approach does not rely on any hidden parameters.
Crosshole traveltime tomography using particle swarm optimization a near-surface field example
(2012)
Particle swarm optimization (PSO) is a relatively new global optimization approach inspired by the social behavior of bird flocking and fish schooling. Although this approach has proven to provide excellent convergence rates in different optimization problems, it has seldom been applied to inverse geophysical problems. Until today, published geophysical applications mainly focus on finding an optimum solution for simple, 1D inverse problems. We have applied PSO-based optimization strategies to reconstruct 2D P-wave velocity fields from crosshole traveltime data sets. Our inversion strategy also includes generating and analyzing a representative ensemble of acceptable models, which allows us to appraise uncertainty and nonuniqueness issues. The potential of our strategy was tested on field data collected at a well-constrained test site in Horstwalde, Germany. At this field site, the shallow subsurface mainly consists of sand- and gravel-dominated glaciofluvial sediments, which, as known from several boreholes and other geophysical experiments, exhibit some well-defined layering at the scale of our crosshole seismic data. Thus, we have implemented a flexible, layer-based model parameterization, which, compared with standard cell-based parameterizations, allows for significantly reducing the number of unknown model parameters and for efficiently implementing a priori model constraints. Comparing the 2D velocity fields resulting from our PSO strategy to independent borehole and direct-push data illustrated the benefits of choosing an efficient global optimization approach. These include a straightforward and understandable appraisal of nonuniqueness issues as well as the possibility of an improved and also more objective interpretation.
In this paper, we provide a comprehensive multivariate cointegration analysis of three parts of the steam coal value chain - export, transport and import prices. The analysis is based on a rich dataset of international coal prices: in particular, we combine data on steam coal prices with freight rates, covering the period December 2001 until August 2009 at weekly frequency. We then test whether the demand and supply side components of steam coal trade are consistently integrated with one another. In addition, export and import prices as well as freight rates for individual trading routes, across regions and globally are combined. We find evidence of significant yet incomplete integration. We also find heterogeneous short-term dynamics of individual markets. Furthermore, we examine whether logistics enter coal price dynamics through transportation costs, which are mainly determined by oil prices. Our results suggest that this is generally not the case.
Ocean Drilling Program (ODP) Site 982 provided a key sediment section at Rockall Plateau for reconstructing northeast Atlantic paleoceanography and monitoring benthic delta O-18 stratigraphy over the late Pliocene to Quaternary onset of major Northern Hemisphere glaciation. A renewed hole-specific inspection of magnetostratigraphic reversals and the addition of epibenthic delta O-18 records for short Pliocene sections in holes 982A, B, and C, crossing core breaks in the delta O-18 record published for Hole 982B, now imply a major revision of composite core depths. After tuning to the orbitally tuned reference record LR04, the new composite delta O-18 record results in a hiatus, where the Kaena magnetic subchron might have been lost, and in a significant age reduction for all proxy records by 130 to 20 ky over the time span 3.2-2.7 million years ago (Ma). Our study demonstrates the general significance of reliable composite-depth scales and delta O-18 stratigraphies in ODP sediment records for generating ocean-wide correlations in paleoceanography. The new concept of age control makes the late Pliocene trends in SST (sea surface temperature) and atmospheric pCO(2) at Site 982 more consistent with various paleoclimate trends published from elsewhere in the North Atlantic.
The perception of internal bodily signals (interoception) plays a relevant role for emotion processing and feelings. This study investigated changes of interoceptive awareness and cardiac autonomic activity induced by short-term food deprivation and its relationship to hunger and affective experience. 20 healthy women were exposed to 24 h of food deprivation in a controlled setting. Interoceptive awareness was assessed by using a heartbeat tracking task. Felt hunger, cardiac autonomic activity, mood and subjective appraisal of interoceptive sensations were assessed before and after fasting. Results show that short-term fasting intensifies interoceptive awareness, not restricted to food cues, via changes of autonomic cardiac and/or cardiodynamic activity. The increase of interoceptive awareness was positively related to felt hunger. Additionally, the results demonstrate the role of cardiac vagal activity as a potential index of emotion related self-regulation, for hunger, mood and the affective appraisal of interoceptive signals during acute fasting.
Particle spectra from acceleration at forward and reverse shocks of young Type Ia Supernova Remnants
(2012)
We study cosmic-ray acceleration in young Type Ia Supernova Remnants (SNRs) by means of test-particle diffusive shock acceleration theory and 1-D hydrodynamical simulations of their evolution. In addition to acceleration at the forward shock, we explore the particle acceleration at the reverse shock in the presence of a possible substantial magnetic field, and consequently the impact of this acceleration on the particle spectra in the remnant. We investigate the time evolution of the spectra for various time-dependent profiles of the magnetic field in the shocked region of the remnant. We test a possible influence on particle spectra of the Alfvenic drift of scattering centers in the precursor regions of the shocks. In addition, we study the radiation spectra and morphology in a broad band from radio to gamma-rays. It is demonstrated that the reverse shock contribution to the cosmic-ray particle population of young Type la SNRs may be significant, modifying the spatial distribution of particles and noticeably affecting the volume-integrated particle spectra in young SNRs. In particular spectral structures may arise in test-particle calculations that are often discussed as signatures of non-linear cosmic-ray modification of shocks. Therefore, the spectrum and morphology of emission, and their time evolution, differ from pure forward-shock solutions.
We use substituted polyanilines for the construction of new polymer electrodes for interaction studies with the redox protein cytochrome c (cyt c) and the enzyme sulfite oxidase (SO). For these purposes four different polyaniline copolymers are chemically synthesized. Three of them are copolymers, containing 2-methoxyaniline-5-sulfonic acid with variable ratios of aniline; the fourth copolymer consists of 3-amino-benzoic acid and aniline. The results show that all polymers are suitable for being immobilized as thin stable films on gold wire and indium tin oxide (ITO) electrode surfaces from DMSO solution. This can be demonstrated by cyclic voltammetry and UV-Vis spectroscopy measurements. Moreover, cyt c can be electrochemically detected not only in solution, but also immobilized on top of the polymer films. Furthermore, the appearance of a significant catalytic current has been demonstrated for the sulfonated polyanilines, when the polymer-coated protein electrode is being measured upon addition of sulfite oxidase, confirming the establishment of a bioanalytical signal chain. Best results have been obtained for the polymer with highest sulfonation grade. The redox switching of the polymer by the enzymatic reaction can also be analyzed by following the spectral properties of the polymer electrode.
The meaning of linguistic connectives has often been characterized in terms of their position in a bipartite (semantic, pragmatic) or a tripartite (content, epistemic, speech act) structure of domains, depending on what kinds of entities are being connected (largely: propositions or speech acts). This paper argues that a more fine-grained analysis can be achieved by directing some more attention to the characterization of the entities being related. We propose an inventory of categories of illocutionary status for labelling the spans that are being connected. On this basis, the distinction between the content and the epistemic domain, in particular, can be made more explicit. Focusing on the group of causal connectives in German, we conducted a corpus annotation study from which we derived distinct pragmatic 'usage profiles' of the most frequent causal connectives. Finally, we offer some suggestions on the role of illocutions in relation-based accounts of discourse structure.
It is well-known that surface plasmon generated near fields of suitably irradiated metal nano-structures can induce a patterning in an azobenzene-modified photosensitive polymer film placed on top. The change in the topography usually follows closely and permanently the underlying near field intensity pattern. With this approach, one can achieve a multitude of morphologies by additionally changing light intensity, polarization and the kind of metal used for nano-structuring. In this paper, we demonstrate that below a critical value of the polymer film thickness, the receding polymer material induces a change in refractive index of the glass-metal-polymer system, modifying the near field intensity distribution and causing a back-reaction on the flow of polymer material. This has a profound influence on the smallest size of topographical features that can be imprinted into the polymer.
We calculate magnetic field fluctuations above a conductor with a nonlocal response (spatial dispersion) and consider a large range of distances. The cross-over from ballistic to diffusive charge transport leads to a reduced noise spectrum at distances below the electronic mean free path, as compared to a local description. We also find that the mean free path provides a lower limit to the correlation (coherence) length of the near field fluctuations. The short-distance behaviour is common to a wide range of materials, including semiconductors and superconductors. Our discussion is aimed at atom chip experiments where spin-flip transitions give access to material properties with mesoscopic spatial resolution. The results also hint at fundamental limits to the coherent operation of miniaturised atom traps and matter-wave interferometers.
We correlate the morphology and energy level alignment of bilayer structures comprising the donor poly(3-hexylthiophene) (P3HT) and the acceptor polyfluorene copolymer poly(9,90dialklylfluorene-alt-4,7-bis(2,5-thiendiyl)-2,1,3-benzothiadiazole) (PFTBTT) with the performance of these bilayers in organic photovoltaic cells (OPVCs). The conducting polymer poly(ethylenedioxythiophene): poly (styrenesulfonate) (PEDT:PSS) was used as the bottom electrode and Ca as the top electrode. Ultraviolet photoelectron spectroscopy (UPS) revealed that notable interface dipoles occur at all interfaces across the OPVC structure, highlighting that vacuum level alignment cannot reliably be used to estimate the electronic properties for device design. Particularly the effective electrode work function values (after contact formation with the conjugated polymers) differ significantly from those of the pristine electrode materials. Chemical reactions between PEDT: PSS and P3HT on the one hand and Ca and PFTBTT on the other hand are identified as cause for the measured interface dipoles. The vacuum level shift between P3HT and PFTBTT is related to mutual energy level pinning at gap states. Annealing induced morphological changes at the P3HT/PFTBTT interface increased the efficiency of OPVCs, while the electronic structure was not affected by thermal treatment.
Hydrological models are commonly used to perform real-time runoff forecasting for flood warning. Their application requires catchment characteristics and precipitation series that are not always available. An alternative approach is nonparametric modelling based only on runoff series. However, the following questions arise: Can nonparametric models show reliable forecasting? Can they perform as reliably as hydrological models? We performed probabilistic forecasting one, two and three hours ahead for a runoff series, with the aim of ascribing a probability density function to predicted discharge using time series analysis based on stochastic dynamics theory. The derived dynamic terms were compared to a hydrological model, LARSIM. Our procedure was able to forecast within 95% confidence interval 1-, 2- and 3-h ahead discharge probability functions with about 1.40 m(3)/s of range and relative errors (%) in the range [-30; 30]. The LARSIM model and the best nonparametric approaches gave similar results, but the range of relative errors was larger for the nonparametric approaches.
This article studies proactive work behavior from a within-person perspective. Building on the broaden-and-build model and the mood-as-information approach, we hypothesized that negative trait affect and positive state affect predict the relative time spent on proactive behavior. Furthermore, based on self-determination theory we argued that persons want to feel competent and that proactive behavior is one way to experience competence. In an experience-sampling study, 52 employees responded to surveys 3 times a day for 5 days. Hierarchical linear modeling confirmed the hypotheses on trait and state affect. Analyses furthermore showed that although a higher level of experienced competence at core task activities was associated with a subsequent increase in time spent on these activities, low experienced competence predicted an increase in time spent on proactive behavior.
Transparent, ion-conducting, luminescent, and flexible ionogels based on the room temperature ionic liquid (IL) 1-butyl-3-methylimidazolium bis(trifluoromethane sulfonyl) imide [Bmim][N(Tf)(2)], a PtEu2 chromophore, and poly(methylmethacrylate) (PMMA) have been prepared. The thermal stability of the PMMA significantly increases with IL incorporation. In particular, the onset weight loss observed at ca. 229 degrees C for pure PMMA increases to 305 degrees C with IL addition. The ionogel has a high ionic conductivity of 10(-3) S cm(-1) at 373 K and exhibits a strong emission in the red with a long average luminescence decay time of tau = 890 mu s. The resulting material is a new type of soft hybrid material featuring useful thermal, optical, and ion transport properties.
The synthesis of ultrafine gold nanoparticles in presence of maltose-modified hyperbranched poly(ethyleneimines) (PEI) is described. The polymer acted as both a reducing and stabilising agent in the particle formation process. The nanoparticles were characterized by means of dynamic light scattering (DLS), transmission electron microscopy (TEM), analytical ultracentrifugation (AUC), small-angle x-ray scattering (SAXS), and small-angle neutron scattering (SANS). The mechanism of nanoparticle formation can be described in two steps. The reduction process of the Au3+ ions located in the inner coil region of the hyperbranched PEI led to the formation of a compact gold core, and is accompanied by a collapse of the polymer coil. Therefore, in the subsequent reduction process a gold-polymer hybrid shell is formed. By using the PEI of higher molar mass, core-shell gold nanoparticles of about 3.6 nm size with a more narrow size distribution and special fluorescence behavior could be synthesized.
Reliability tests for wavelength-stabilized compact diode laser systems emitting at 671 nm are presented. The devices were mounted on microoptical benches with the dimensions of 13 mm x 4 mm. Reflecting Bragg gratings were used for wavelength stabilization and emission width narrowing. The reliability tests were performed at 25 degrees C and at an output power up to 10 mW per micrometer stripe width of the gain medium. Reliable operation could be demonstrated over a test time up to 14 500 h at an output power up to 1.0 W. Environmental tests using random vibrations with acceleration up to 29 g were performed without deterioration of the devices.
Carbon-based ionogels tuning the properties of the ionic liquid via carbon-ionic liquid interaction
(2012)
The behavior of two ionic liquids (ILs), 1-ethyl-3-methylimidazolium dicyanamide [Emim][DCA] and 1-ethyl-3-methylimidazolium triflate [Emim][TfO], in (meso) porous carbonaceous hosts was investigated. Prior to IL incorporation into the host, the carbon matrix was thermally annealed between 180 and 900 degrees C to control carbon condensation and surface chemistry. The resulting materials have an increasing "graphitic'' carbon character with increasing treatment temperature, reflected in a modified behavior of the ILs when impregnated into the carbon host. The two ILs show significant changes in the thermal behavior as measured from differential scanning calorimetry; these changes can be assigned to anion-pi interaction between the IL anions and the pore wall surfaces of these flexible carbonaceous support materials.
Hybrid magnetic nanoparticles (mgNP) with a magnetite core diameter of 10 +/- 1 nm surface functionalized with oligo(omega-pentadecalactone) (OPDL) oligomers with M-n between 1300 and 3300 g mol(-1) could be successfully prepared having OPDL grafted from 200 mg g(-1) to 2170 mg g(-1). The particles are dispersible in chloroform resulting in stable suspensions. Magnetic response against an external magnetic field proved the superparamagnetic nature of the particles with a low coercivity (B-c) value of 297 mu T. The combination of the advantageous superparamagnetism of the mgNP with the exceptional stability of OPDL makes these novel hybrid mgNP promising candidates as multifunctional building blocks for magnetic nanocomposites with tunable physical properties.
Mesoporous, highly structured silicon carbide (beta-SiC) was synthesised from renewable plant materials (two Equisetaceae species) in a one-step carbothermal process at remarkably low temperatures down to 1200 degrees C. The SiC precursor is a silicon-carbon mixture with finely dispersed carbon prepared by pyrolysis of the organic plant matrix. Yields are 3 to 100% (omega(Si/Si) related to the silicon deposited in the plant material), depending on reaction temperature and time. IR spectroscopy, X-ray diffraction, and nitrogen sorption prove the formation of high-purity beta-SiC with minor inorganic impurities after purification and a high specific surface area of up to 660 m(2) g(-1). Scanning electron microscopy shows that the plant morphology is maintained in the final SiC. Sedimentation analysis finds a mean particle size (diameters d(50)) of 20 mu m.
It is well known that the spacetime diagrams of some cellular automata have a self-similar fractal structure: for instance Wolfram's rule 90 generates a Sierpinski triangle. Explaining the self-similarity of the spacetime diagrams of cellular automata is a well-explored topic, but virtually all of the results revolve around a special class of automata, whose typical features include irreversibility, an alphabet with a ring structure, a global evolution that is a ring homomorphism, and a property known as (weakly) p-Fermat. The class of automata that we study in this article has none of these properties. Their cell structure is weaker, as it does not come with a multiplication, and they are far from being p-Fermat, even weakly. However, they do produce self-similar spacetime diagrams, and we explain why and how.
This editorial introduces a set of papers on differential embodiment in spatial tasks. According to the theoretical notion of embodied cognition, our experiences of acting in the world, and the constraints of our sensory and motor systems, strongly shape our cognitive functions. In the current set of papers, the authors were asked to particularly consider idiosyncratic or differential embodied cognition in the context of spatial tasks and processes. In each contribution, differential embodiment is considered from one of two complementary perspectives: either by considering unusual individuals, who have atypical bodies or uncommon experiences of interacting with the world; or by exploring individual differences in the general population that reflect the naturally occurring variability in embodied processes. Our editorial summarizes the contributions to this special issue and discusses the insights they offer. We conclude from this collection of papers that exploring differences in the recruitment and involvement of embodied processes can be highly informative, and can add an extra dimension to our understanding of spatial cognitive functions. Taking a broader perspective, it can also shed light on important theoretical and empirical questions concerning the nature of embodied cognition per se.
The switching kinetics of thin thermo-responsive hydrogel films of poly(monomethoxy-diethyleneglycol-acrylate) (PMDEGA) are investigated. Homogeneous and smooth PMDEGA films with a thickness of 35.9 nm are prepared on silicon substrates by spin coating. As probed with white light interferometry, PMDEGA films with a thickness of 35.9 nm exhibit a phase transition temperature of the lower critical solution temperature (LCST) type of 40 degrees C. In situ neutron reflectivity is performed to investigate the thermo-responsive behavior of these PMDEGA hydrogel films in response to a sudden thermal stimulus in deuterated water vapor atmosphere. The collapse transition proceeds in a complex way which can be seen as three steps. The first step is the shrinkage of the initially swollen film by a release of water. In the second step the thickness remains constant with water molecules embedded in the film. In the third step, perhaps due to a conformational rearrangement of the collapsed PMDEGA chains, water is reabsorbed from the vapor atmosphere, thereby giving rise to a relaxation process. Both the shrinkage and relaxation processes can be described by a simple model of hydrogel deswelling.
The trade-off between predation risk and the need to feed is one of the major constraints animals have to cope with. Virtually all animals have a higher risk of being preyed upon when being active (e.g., searching for food or mating partners), compared with being inactive (e.g., staying at their burrows, nests, etc.). Yet, staying safe leads to a higher risk of starvation and may reduce reproductive success and body growth. Hence selection on behaviour optimizing the search, handling and digestion of food while avoiding the risk of predation is strong and should lead to strategies maximising survival chances and inclusive fitness. These facts call for integrative studies manipulating both, abundance of food and predation risk in a factorial set up, analysing the effects of both factors on behaviour and physiological parameters. We present results of a 2 x 2 factorial experiment, manipulating risk of predation and food abundance in guppies. We found that the two factors have an additive effect on body growth, but that predation risk by a pike cichlid is the main factor affecting the expression of behavioural strategies in guppies. Low food availability and high predation risk led to lower body growth. High predation risk affected swimming depth and risk sensitivity of guppies and might represent adaptive behavioural changes to the environmental context experienced in early life. Our study shows that integrative studies, analysing multiple interdependent and interconnected factors in the wild and in the lab are needed to further understand animal behaviour and development.
Today, serious health problems as overweight and obesity are not just constricted to the developed world, but also increase in the developing countries (Prentice 2006, Ramachandram et al. 2002). Focusing on this issue, BMI and percentage of body fat were compared in 2094 schoolchildren from two cross-sectional studies from India and Germany investigated in 2008 and 2009. The German children are in all age groups significantly taller, whereas the Indian children show higher values in BMI (e.g. 12 years: Indian: around 22 kg/m(2); German: around 19 kg/m(2)) and in the percentage of body fat (e.g. 12 years: Indian: around 27 %; German: around 18-20%) in most of the investigated age groups. The Indian children have significantly higher BMI between 10 and 13 (boys) respectively 14 years (girls). Indian children showed significant higher percentage of body fat between 10 and 15 years (boys) and between 8 and 16 years (girls). The difference in overweight between Indian and German children was strongest at 11 (boys) and 12 (girls) years: 70 % of the Indian but 20% of the German children were classified as overweight. In countries such as India that undergo nutritional transition, a rapid increase in obesity and overweight is observed. In contrast to the industrialized countries, the risk of overweight in developing countries is associated with high socioeconomic status. Other reasons of the rapid increase of overweight in the developing countries caused by different environmental or genetic factors are discussed.
Auxology has developed from mere describing child and adolescent growth into a vivid and interdisciplinary research area encompassing human biologists, physicians, social scientists, economists and biostatisticians. The meeting illustrated the diversity in auxology, with the various social, medical, biological and biostatistical aspects in studies on child growth and development.
Hybrid terrains are a convenient approach for the representation of digital terrain models, integrating heterogeneous data from different sources. In this article, we present a general, efficient scheme for achieving interactive level-of-detail rendering of hybrid terrain models, without the need for a costly preprocessing or resampling of the original data. The presented method works with hybrid digital terrains combining regular grid data and local high-resolution triangulated irregular networks. Since grid and triangulated irregular network data may belong to different datasets, a straightforward combination of both geometries would lead to meshes with holes and overlapping triangles. Our method generates a single multiresolution model integrating the different parts in a coherent way, by performing an adaptive tessellation of the region between their boundaries. Hence, our solution is one of the few existing approaches for integrating different multiresolution algorithms within the same terrain model, achieving a simple interactive rendering of complex hybrid terrains.
Multifunctional chain transfer agents for RAFT polymerisation were designed for the one-step synthesis of amphiphilic star polymers. Thus, hydrophobically end-capped 3- and 4-arm star polymers, as well as linear ones for reference, were made of the hydrophilic monomer N,N-dimethylacrylamide (DMA) in high yield with molar masses up to 150 000 g mol(-1), narrow molar mass distribution (PDI <= 1.2) and high end group functionality (similar to 90%). The associative telechelic polymers form transient networks of interconnected aggregates in aqueous solution, thus acting as efficient viscosity enhancers and rheology modifiers, eventually forming hydrogels. The combination of dynamic light scattering (DLS), small angle neutron scattering (SANS) and rheology experiments revealed that several molecular parameters control the structure and therefore the physical properties of the aggregates. In addition to the size of the hydrophilic block (maximum length for connection) and the length of the hydrophobic alkyl chain ends (stickiness), the number of arms (functionality) proved to be a key parameter.
Developments of future scenarios of Antarctic ecosystems are still in their infancy, whilst predictions of the physical environment are recognized as being of global relevance and corresponding models are under continuous development. However, in the context of environmental change simulations of the future of the Antarctic biosphere are increasingly demanded by decision makers and the public, and are of fundamental scientific interest. This paper briefly reviews existing predictive models applied to Antarctic ecosystems before providing a conceptual framework for the further development of spatially and temporally explicit ecosystem models. The concept suggests how to improve approaches to relating species' habitat description to the physical environment, for which a case study on sea urchins is presented. In addition, the concept integrates existing and new ideas to consider dynamic components, particularly information on the natural history of key species, from physiological experiments and biomolecular analyses. Thereby, we identify and critically discuss gaps in knowledge and methodological limitations. These refer to process understanding of biological complexity, the need for high spatial resolution oceanographic data from the entire water column, and the use of data from biomolecular analyses in support of such ecological approaches. Our goal is to motivate the research community to contribute data and knowledge to a holistic, Antarctic-specific, macroecological framework. Such a framework will facilitate the integration of theoretical and empirical work in Antarctica, improving our mechanistic understanding of this globally influential ecoregion, and supporting actions to secure this biodiversity hotspot and its ecosystem services.
In this work the adsorption of CO2 and CH4 on a series of isoreticular microporous metal-organic frameworks based on 2-substituted imidazolate-4-amide-5-imidates, IFP-1-IFP-6 (IFP Imidazolate Framework Potsdam), is studied firstly by pure gas adsorption at 273 K. All experimental isotherms can be nicely described by using the Toth isotherm model and show the preferred adsorption of CO2 over CH4. At low pressures the Toth isotherm equation exhibits a Henry region, wherefore Henry's law constants for CO2 and CH4 uptake could be determined and ideal selectivity (alpha CO2/CH4) has been calculated. Secondly, selectivities were calculated from mixture data by using nearly equimolar binary mixtures of both gases by a volumetric-chromatographic method to examine the IFPs. Results showed the reliability of the selectivity calculation. Values of (alpha CO2/CH4) around 7.5 for IFP-5 indicate that this material shows much better selectivities than IFP-1, IFP-2, IFP-3, IFP-4 and IFP-6 with slightly lower selectivity (alpha CO2/CH4) = 4-6. The preferred adsorption of CO2 over CH4 especially of IFP-5 and IFP-4 makes these materials suitable for gas separation application.
Channel transmission losses in drylands take place normally in extensive alluvial channels or streambeds underlain by fractured rocks. They can play an important role in streamflow rates, groundwater recharge, freshwater supply and channel-associated ecosystems. We aim to develop a process-oriented, semi-distributed channel transmission losses model, using process formulations which are suitable for data-scarce dryland environments and applicable to both hydraulically disconnected losing streams and hydraulically connected losing(/gaining) streams. This approach should be able to cover a large variation in climate and hydro-geologic controls, which are typically found in dryland regions of the Earth. Our model was first evaluated for a losing/gaining, hydraulically connected 30 km reach of the Middle Jaguaribe River (MJR), Ceara, Brazil, which drains a catchment area of 20 000 km(2). Secondly, we applied it to a small losing, hydraulically disconnected 1.5 km channel reach in the Walnut Gulch Experimental Watershed (WGEW), Arizona, USA. The model was able to predict reliably the streamflow volume and peak for both case studies without using any parameter calibration procedure. We have shown that the evaluation of the hypotheses on the dominant hydrological processes was fundamental for reducing structural model uncertainties and improving the streamflow prediction. For instance, in the case of the large river reach (MJR), it was shown that both lateral stream-aquifer water fluxes and groundwater flow in the underlying alluvium parallel to the river course are necessary to predict streamflow volume and channel transmission losses, the former process being more relevant than the latter. Regarding model uncertainty, it was shown that the approaches, which were applied for the unsaturated zone processes (highly nonlinear with elaborate numerical solutions), are much more sensitive to parameter variability than those approaches which were used for the saturated zone (mathematically simple water budgeting in aquifer columns, including backwater effects). In case of the MJR-application, we have seen that structural uncertainties due to the limited knowledge of the subsurface saturated system interactions (i.e. groundwater coupling with channel water; possible groundwater flow parallel to the river) were more relevant than those related to the subsurface parameter variability. In case of the WEGW application we have seen that the non-linearity involved in the unsaturated flow processes in disconnected dryland river systems (controlled by the unsaturated zone) generally contain far more model uncertainties than do connected systems controlled by the saturated flow. Therefore, the degree of aridity of a dryland river may be an indicator of potential model uncertainty and subsequent attainable predictability of the system.
Monsoon systems around the world are governed by the so-called moisture-advection feedback. Here we show that, in a minimal conceptual model, this feedback implies a critical threshold with respect to the atmospheric specific humidity q(o) over the ocean adjacent to the monsoon region. If q(o) falls short of this critical value q(o)(c), monsoon rainfall over land cannot be sustained. Such a case could occur if evaporation from the ocean was reduced, e.g. due to low sea surface temperatures. Within the restrictions of the conceptual model, we estimate q(o)(c) from present-day reanalysis data for four major monsoon systems, and demonstrate how this concept can help understand abrupt variations in monsoon strength on orbital timescales as found in proxy records.
The zoom lens of attention simulating shuffled versus normal text reading using the SWIFT model
(2012)
Assumptions on the allocation of attention during reading are crucial for theoretical models of eye guidance. The zoom lens model of attention postulates that attentional deployment can vary from a sharp focus to a broad window. The model is closely related to the foveal load hypothesis, i.e., the assumption that the perceptual span is modulated by the difficulty of the fixated word. However, these important theoretical concepts for cognitive research have not been tested quantitatively in eye movement models. Here we show that the zoom lens model, implemented in the SWIFT model of saccade generation, captures many important patterns of eye movements. We compared the model's performance to experimental data from normal and shuffled text reading. Our results demonstrate that the zoom lens of attention might be an important concept for eye movement control in reading.
Recently observed large-scale disintegration of Antarctic ice shelves has moved their fronts closer towards grounded ice. In response, ice-sheet discharge into the ocean has accelerated, contributing to global sea-level rise and emphasizing the importance of calving-front dynamics. The position of the ice front strongly influences the stress field within the entire sheet-shelf-system and thereby the mass flow across the grounding line. While theories for an advance of the ice-front are readily available, no general rule exists for its retreat, making it difficult to incorporate the retreat in predictive models. Here we extract the first-order large-scale kinematic contribution to calving which is consistent with large-scale observation. We emphasize that the proposed equation does not constitute a comprehensive calving law but represents the first-order kinematic contribution which can and should be complemented by higher order contributions as well as the influence of potentially heterogeneous material properties of the ice. When applied as a calving law, the equation naturally incorporates the stabilizing effect of pinning points and inhibits ice shelf growth outside of embayments. It depends only on local ice properties which are, however, determined by the full topography of the ice shelf. In numerical simulations the parameterization reproduces multiple stable fronts as observed for the Larsen A and B Ice Shelves including abrupt transitions between them which may be caused by localized ice weaknesses. We also find multiple stable states of the Ross Ice Shelf at the gateway of the West Antarctic Ice Sheet with back stresses onto the sheet reduced by up to 90 % compared to the present state.
A partial transformation alpha on an n-element chain X-n is called order-preserving if x <= y implies x alpha <= y alpha for all x, y in the domain of alpha and it is called extensive if x <= x alpha for all x in the domain of alpha. The set of all partial order-preserving extensive transformations on X-n forms a semiband POEn. We determine the maximal subsemigroups as well as the maximal subsemibands of POEn.
New hybrid materials have been prepared by grafting synthetic peptides in the interlayer spacing of Cu(II) and Co(II) layered simple hydroxides (LSHs). The interlayer spacing of the hybrids depends on the peptide chain length; the dependence is specific for the copper and cobalt-based hybrids. This suggests a metal-or LSH-specific interaction of the peptides with the respective inorganic layers. When tyrosine is present in the peptide, its fluorescence is quenched after grafting the peptide to the LSH. Studies of the luminescence vs. pH indicate deprotonation of the tyrosine moieties to tyrosinate at high pH, accompanied by the onset of luminescence. The luminescence increases with increasing OH- concentration, suggesting an application of the hybrids as chemical sensors. Moreover, the peptides influence the magnetic properties of the hybrids. The copper-based hybrids behave antiferromagnetically and the cobalt-based hybrids are ferrimagnets.
Flavins are chromophores in light-gated enzymes and therefore central in many photobiological processes. To unravel the optical excitation process as the initial, elementary step towards signal transduction, detailed ultrafast (femtosecond) experiments probing the photo-activation of flavins have been carried out recently [Weigel et al., J. Phys. Chem. B, 2011, 115, 3656-3680.]. The present paper contributes to a further understanding and interpretation of these experiments by studying the post-excitation vibrational dynamics of riboflavin (RF) and microsolvated riboflavin, RF center dot 4H(2)O, using first principles non-adiabatic molecular dynamics. By analyzing the characteristic atom motions and calculating time-resolved stimulated emission spectra following pi pi* excitation, it is found that after optical excitation C-N and C-C vibrations in the isoalloxazine rings of riboflavin set in. The Franck-Condon (vertically excited) state decays within about 10 fs, in agreement with experiment. Anharmonic coupling leads to Intramolecular Vibrational energy Redistribution (IVR) on the timescale of about 80-100 fs, first to (other) C-C stretching modes of the isoalloxazine rings, then by energy spread over the whole molecule, including low-frequency in-plane modes. The IVR is accompanied by a red-shift and broadening of the emission spectrum. When RF is microsolvated with four water molecules, an overall redshift of optical spectra by about 20 nm is observed but the relaxation dynamics is only slightly affected. For several trajectories, a tendency for hydrogen transfer from water to flavin-nitrogen (N-5) was found.
Phytoplankton development affects the community structure and dynamics of freshwater bacteria by changing the availability of nutrients, algal exudates and biological surfaces. To elucidate these effects of phytoplankton development in spring in oligotrophic Lake Stechlin (Germany), we measured limnological and biological parameters, including the bacterial community composition (BCC), at the depth of the highest chlorophyll a concentration. To increase the resolution of BCC measurements, we separated particle-associated (PA) and free-living (FL) bacteria using serial filtration through 5.0 and 0.2 mu m pore size filters, respectively. The BCC of ultramicrobacteria was also determined by collecting the 0.2 mu m filtrate on 0.1 mu m filters. Changes in the community composition of Bacteria and particularly of Actinobacteria, one of the most important bacterial groups in temperate freshwater habitats, were studied via DGGE analysis of PCR-amplified 16S rRNA gene fragments. Patterns in BCC dynamics of FL Bacteria and Actinobacteria remained fairly constant throughout the study period, while patterns of PA Bacteria were more variable over time. At the breakdown of the diatom spring bloom, bacterial production and abundance sharply increased, indicating a close coupling between heterotrophic bacteria and algal detritus. The succession in BCC revealed life-style dependent patterns related to specific environmental variables. Our results indicate independent dynamics of PA and FL Bacteria as well as Actinobacteria during succession of phytoplankton spring blooms. These differences in bacterial lifestyle can only be resolved when the PA and FL fractions of microorganisms are separated.
This article deals with Spanish modal adverbs and verbs of cognitive attitude (Capelli 2007) and their epistemic and/or evidential use. The article is based upon the hypothesis that the study of the use of these linguistic devices has to be highly context-sensitive, as it is not always (only) the sentence level that has to be looked at if one wants to find out whether a certain adverb or verb of cognitive attitude is used evidentially or epistemically. In this article, therefore, the context is used to determine which meaning aspects of an element are encoded and which are contributed by the context. The data were retrieved from the daily newspaper El Pais. Nevertheless, the present study is not a quantitative one, but rather a qualitative study. My corpus analysis indicates that it is not possible to differentiate between the linguistic categories of evidentiality and epistemic modality in every case, although it indeed is possible in the vast majority of cases. In verbs of cognitive attitude, evidentiality and epistemic modality seem to be two interwoven categories, while concerning modal adverbs it is usually possible to separate the categories and to distinguish between the different subtypes of evidentiality such as visual evidence, hearsay and inference.
Lazy graph transformation
(2012)
Applying an attributed graph transformation rule to a given object graph always implies some kind of constraint solving. In many cases, the given constraints are almost trivial to solve. For instance, this is the case when a rule describes a transformation G double right arrow H, where the attributes of H are obtained by some simple computation from the attributes of G. However there are many other cases where the constraints to solve may be not so trivial and, moreover, may have several answers. This is the case, for instance, when the transformation process includes some kind of searching. In the current approaches to attributed graph transformation these constraints must be completely solved when defining the matching of the given transformation rule. This kind of early binding is well-known from other areas of Computer Science to be inadequate. For instance, the solution chosen for the constraints associated to a given transformation step may be not fully adequate, meaning that later, in the search for a better solution, we may need to backtrack this transformation step.
In this paper, based on our previous work on the use of symbolic graphs to deal with different aspects related with attributed graphs, including attributed graph transformation, we present a new approach that, based on the new notion of narrowing graph transformation rule, allows us to delay constraint solving when doing attributed graph transformation, in a way that resembles lazy computation. For this reason, we have called lazy this new kind of transformation. Moreover, we show that the approach is sound and complete with respect to standard attributed graph transformation. A running example, where a graph transformation system describes some basic operations of a travel agency, shows the practical interest of the approach.
Graph transformation systems have been studied extensively and applied to several areas of computer science like formal language theory, the modeling of databases, concurrent or distributed systems, and visual, logical, and functional programming. In most kinds of applications it is necessary to have the possibility of restricting the applicability of rules. This is usually done by means of application conditions. In this paper, we continue the work of extending the fundamental theory of graph transformation to the case where rules may use arbitrary (nested) application conditions. More precisely, we generalize the Embedding theorem, and we study how local confluence can be checked in this context. In particular, we define a new notion of critical pair which allows us to formulate and prove a Local Confluence Theorem for the general case of rules with nested application conditions. All our results are presented, not for a specific class of graphs, but for any arbitrary M-adhesive category, which means that our results apply to most kinds of graphical structures. We demonstrate our theory on the modeling of an elevator control by a typed graph transformation system with positive and negative application conditions.
Clustering of gene expression data is often done with the latent aim of dimension reduction, by finding groups of genes that have a common response to potentially unknown stimuli. However, what is poorly understood to date is the behaviour of a low dimensional signal embedded in high dimensions. This paper introduces a multicollinear model which is based on random matrix theory results, and shows potential for the characterisation of a gene cluster's correlation matrix. This model projects a one dimensional signal into many dimensions and is based on the spiked covariance model, but rather characterises the behaviour of the corresponding correlation matrix. The eigenspectrum of the correlation matrix is empirically examined by simulation, under the addition of noise to the original signal. The simulation results are then used to propose a dimension estimation procedure of clusters from data. Moreover, the simulation results warn against considering pairwise correlations in isolation, as the model provides a mechanism whereby a pair of genes with 'low' correlation may simply be due to the interaction of high dimension and noise. Instead, collective information about all the variables is given by the eigenspectrum.
An assisted tandem catalytic transformation of diallyl amines and diallyl ethers into N-aryl pyrroles and furans, respectively, is described. The sequence relies on ring closing metathesis followed by dehydrogenation of the initially formed dihydropyrroles and dihydrofurans. Both steps are Ru-catalyzed, but the sequence requires only one precatalyst, because conversion of the metathesis catalyst into the dehydrogenation catalyst is achieved in situ, triggered by the oxidant tert-butyl hydroperoxide.
Despite global warming and unlike their Himalayan neighbours, glaciers in the Karakoram mountains do not show signs of significant retreat. Here we report high velocity variations of Biafo Glacier, central Karakoram, which occurred between 2001 and 2009 and which indicate considerable dynamics in its flow behaviour. We have generated a dense time series of glacier surface velocities, based on cross-correlation of optical satellite images, which clearly shows seasonal and interannual velocity variations, reaching 50% in some places. The interannual velocity variations resemble the passing of a broad wave of high velocities, with peak velocities during 2005 and some diffusion down-glacier over a period of at least 4 years. High interannual velocity variations are also observed at other glaciers in the vicinity, suggesting a common cause, although these appear to partly comprise longer acceleration phases. Analysis of weather station data provides some indications of meteorological conditions that could have promoted sustained sliding events during this period, but this does not explain the wave-like nature of the acceleration at Biafo Glacier, and the regular, protracted velocity changes.
The Antarctic terrestrial environment is under increasing pressure from human activities. The Fildes Region is characterized by high biodiversity, but is also a major logistic centre for the northern Antarctic Peninsula. Different interests, from scientific research, nature conservation, protection of geological and historical values, station operations, transport logistics and tourism, regularly overlap in space and time. This has led to increasing conflict among the multiple uses of the region and breaches of the legal requirements for environmental protection that apply in the area. The aim of this study was to assess the impacts of human activities in the Fildes Region by monitoring the distribution of bird and seal breeding sites and recording human activities and their associated environmental impacts. Data from an initial monitoring period 2003-06 were compared with data from 2008-10. We observed similar or increased levels of air, land and ship traffic, but fewer violations of overflight limits near Antarctic Specially Protected Area No. 150 Ardley Island. Open waste dumping and oil contamination are still major environmental impacts. Scientific and outdoor leisure activities undertaken by station personnel are more frequent than tourist activities and are likely to have a commensurate level of environmental impact. Despite the initial success of some existing management measures, it is essential that scientific and environmental values continue to be safeguarded, otherwise environmental impacts will increase and the habitat will be further degraded. We argue that the Fildes Region should be considered for designation as an Antarctic Specially Managed Area, a measure that has proven effective for environmental management of vulnerable areas of the Antarctic.
Disturbances are characteristic for many ecosystems. However, we still lack generalizations concerning their role in shaping communities, particularly when disturbances co-occur. To study such effects, we used a novel modeling approach that is unrestricted by a priori tradeoffs among specific plant traits, except for those generated by allocation principles. Thus, trait combinations were emergent properties associated with biotic and abiotic constraints. Specifically, we asked which traits dominate under specific disturbance regimes, whether single and combined disturbance regimes promote similar trait tradeoffs and how complex disturbance regimes affect species richness and functional diversity. Overall, disturbances' temporal properties governed the outcome of combined disturbances and were a stronger assortative force than spatial disturbance properties: low temporal predictability decreased seed-dispersability and dormancy, but increased competitive ability and disturbance tolerance. Evidence for tradeoffs between different colonization modes and between dormancy and disturbance tolerance were found, while surprisingly, the widely accepted colonization-competition tradeoff was not generated. Diversity was highest at intermediate disturbance intensity, but decreased monotonically with increasing unpredictability. In accordance with our results, future models should avoid restrictive assumptions about tradeoffs to generate robust and more general predictions about the role of disturbances for community dynamics.
Background: The renin-angiotensin-aldosterone system (RAAS) is involved in the pathogenesis of insulin resistance and type 2 diabetes in the general population. The RAAS is activated during pregnancy. However, it is unknown whether the RAAS contributes to glycemia in pregnant women.
Methods: Plasma renin activity (PRA) and plasma aldosterone levels were quantified at delivery in 689 Chinese mothers. An oral glucose tolerance test in fasted women was performed in the second trimester of pregnancy. The diagnosis of gestational diabetes mellitus (GDM) and impaired glucose tolerance during pregnancy were made according to the guidelines of the Chinese Society of Obstetrics.
Results: Plasma aldosterone was significantly higher in pregnant women with GDM as compared to those without impairment of glycemic control (normal pregnancies: 0.27 +/- 0.21 ng/mL, GDM: 0.36 +/- 0.30 ng/mL; p<0.05). Regression analyses revealed that PRA was negatively correlated with fasting blood glucose (FBG) (R-2 = 0.03, p = 0.007), whereas plasma aldosterone and aldosterone/PRA ratio were positively correlated with FBG (R-2 = 0.05, p<0.001 and R-2 = 0.03, p = 0.007, respectively). Multivariable regression analysis models considering relevant confounding factors confirmed these findings.
Conclusions: This study demonstrated that fasting blood glucose in pregnant women is inversely correlated with the PRA, whereas plasma aldosterone showed a highly significant positive correlation with fasting blood glucose during pregnancy. Moreover, plasma aldosterone is significantly higher in pregnant women with GDM as compared to those women with normal glucose tolerance during pregnancy. Although causality cannot be proven in association studies, these data may indicate that the RAAS during pregnancy contributes to the pathogenesis of insulin resistance/new onset of diabetes during pregnancy.
The surface of single-walled carbon nanotubes (SWCNTs) was functionalized with azide-terminated poly(vinylidene fluoride) (PVDF). Functionalization was confirmed by dispersibility, Raman spectroscopy, and thermogravimetric analyses. Raman spectra show disordering of the SWCNTs, thus, strongly suggesting that PVDF was covalently attached to SWCNTs. Functionalized SWCNTs were mixed with commercially available PVDF in a twin-screw extruder and thin films were obtained by melt-pressing. Films containing 0.5 and 1 wt% PVDF-functionalized SWCNTs exhibited significantly improved electrical conductivity compared to PVDF films containing pristine SWCNTs.
Rates of multiple paternities were investigated in the sailfin molly (Poecilia latipinna), using eight microsatellite loci. Genotyping was performed for offspring and mothers in 40 broods from four allopatric populations from the south-eastern U.S.A. along a geographic stretch of 1200 km in west-east direction and approximately 200 km from north to south. No significant differences regarding rates of multiple paternities were found between populations despite sample populations stemming from ecologically divergent habitats. Even the most conservative statistical approach revealed a minimum of 70% of the broods being sired by at least two males, with an average of 1.80-2.95 putative fathers per brood. Within broods, one male typically sired far more offspring than would be expected under an assumed equal probability of all detected males siring offspring.
This study examined the effects of competing speech on auditory semantic comprehension using a dichotic sentence-word priming paradigm. Lexical decision performance for target words presented in spoken sentences was compared in strongly and weakly biasing semantic contexts. Targets were either congruent or incongruent with the sentential bias. Sentences were presented to one auditory channel (right or left), either in isolation or with competing speech produced by a single talker of the same gender presented simultaneously. The competing speech signal was either presented in the same auditory channel as the sentence context, or in a different auditory channel, and was either meaningful (played forward) or unintelligible (time-reversed).
Biasing contexts presented in isolation facilitated responses to congruent targets and inhibited responses to incongruent targets, relative to a neutral baseline. Facilitation priming was reduced or eliminated by competing speech presented in the same auditory channel, supporting previous findings that semantic activation is highly sensitive to the intelligibility of the context signal. Competing speech presented in a different auditory channel affected facilitation priming differentially depending upon ear of presentation, suggesting hemispheric differences in the processing of the attended and competing signals. Results were consistent with previous claims of a right ear advantage for meaningful speech, as well as with visual word recognition findings implicating the left hemisphere in the generation of semantic predictions and the right hemisphere in the integration of newly encountered words into the sentence-level meaning. Unlike facilitation priming, inhibition was relatively robust to the energetic and informational masking effects of competing speech and was not influenced by the strength of the contextual bias or the meaningfulness of the competing signal, supporting a two-process model of sentence priming in which inhibition reflects later-stage, expectancy-driven strategic processes that may benefit from perceptual reanalysis after initial semantic activation.
Mesoporous carbon/iron carbide hybrid materials with surface areas reaching 800 m(2) g(-1) were synthesized via an exotemplating route using monolithic mesoporous silica as template and the ionic liquid 1-butyl-3-methylimidazolium tetrachloridoferrate(III) [Bmim][FeCl4] as carbon and iron source. After heat treatment (750 degrees C under argon) of the [Bmim][FeCl4] precursor confined within the silica matrix, the silica exotemplate was removed with HF leaving the mesoporous C/Fe3C hybrid behind. The surface areas and the pore sizes depend on the exotemplate and the surface areas a significantly larger than any other surface area reported for C/Fe3C hybrid materials so far. The approach is thus a prototype for the synthesis of high-surface area iron carbide-based hybrid materials with potential application in catalysis.
In both eukaryotic and prokaryotic DNA sequences of 30-100 base-pairs rich in AT base-pairs have been identified at which the double helix preferentially unwinds. Such DNA unwinding elements are commonly associated with origins for DNA replication and transcription, and with chromosomal matrix attachment regions. Here we present a quantitative study of local DNA unwinding based on extensive single DNA plasmid imaging. We demonstrate that long-lived single-stranded denaturation bubbles exist in negatively supercoiled DNA, at the expense of partial twist release. Remarkably, we observe a linear relation between the degree of supercoiling and the bubble size, in excellent agreement with statistical modelling. Furthermore, we obtain the full distribution of bubble sizes and the opening probabilities at varying salt and temperature conditions. The results presented herein underline the important role of denaturation bubbles in negatively supercoiled DNA for biological processes such as transcription and replication initiation in vivo.