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Although intensification of toxic cyanobacterial blooms over the last decade is a matter of growing concern due to bloom impact on water quality, the biological role of most of the toxins produced is not known. In this critical review we focus primarily on the biological role of two toxins, microcystins and cylindrospermopsin, in inter- and intra-species communication and in nutrient acquisition. We examine the experimental evidence supporting some of the dogmas in the field and raise several open questions to be dealt with in future research. We do not discuss the health and environmental implications of toxin presence in the water body.
Ciliate epibionts associated with crustacean zooplankton are widespread in aquatic systems, but their ecological roles are little known. We studied the occurrence of ciliate epibionts on crustacean zooplankton in nine German lakes with different limnological features during the summer of 2011. We also measured the detachment and re-attachment rates of the ciliates, changes in their motility, and the feeding rates of attached vs. detached ciliate epibionts. Epibionts were found in all lakes sampled except an acidic lake with large humic inputs. Epibiont prevalence was as high as 80.96% on the cladoceran Daphnia cucullata, 67.17% on the cladoceran Diaphanosoma brachyurum, and 46.67% on the calanoid copepod Eudiaptomus gracilis. Both cladoceran groups typically had less than 10 epibionts per individual, while the epibiont load on E. gracilis ranged from 1 to >30 epibionts per individual. After the death of the zooplankton host, the peritrich ciliate epibiont Epistylis sp. detached in an exponential fashion with a half-life of 5 min, and 98% detached within 30 min, leaving behind the stalks used for attachment. Immediately after detachment, the ciliates were immotile, but 62% became motile within 60 min. When a new host was present, only 27% reattached after 120 min. The average measured ingestion rate and clearance rate of Epistylis were 11,745 bacteria ciliate(-1) h(-1) and 24.33 mu l ciliate(-1) h(-1), respectively. Despite their high feeding rates, relatively low epibiont abundances were observed in the field, which suggests either diversion of energy to stalk formation, high metabolic loss by the epibionts, or high mortality among the epibiont populations.
Direct observations, satellite measurements and paleo records reveal strong variability in the Atlantic subpolar gyre on various time scales. Here we show that variations of comparable amplitude can only be simulated in a coupled climate model in the proximity of a dynamical threshold. The threshold and the associated dynamic response is due to a positive feedback involving increased salt transport in the subpolar gyre and enhanced deep convection in its centre. A series of sensitivity experiments is performed with a coarse resolution ocean general circulation model coupled to a statistical-dynamical atmosphere model which in itself does not produce atmospheric variability. To simulate the impact of atmospheric variability, the model system is perturbed with freshwater forcing of varying, but small amplitude and multi-decadal to centennial periodicities and observational variations in wind stress. While both freshwater and wind-stress-forcing have a small direct effect on the strength of the subpolar gyre, the magnitude of the gyre's response is strongly increased in the vicinity of the threshold. Our results indicate that baroclinic self-amplification in the North Atlantic ocean can play an important role in presently observed SPG variability and thereby North Atlantic climate variability on multi-decadal scales.
Population fragmentation is often correlated with loss of genetic diversity and reduced fitness. Obligate out-crossing (dioecy) is expected to enhance genetic diversity, reduce genetic differentiation, and avoid inbreeding depression through frequent gene flow. However, in highly fragmented populations dioecy has only diminishing effects upon genetic structure as pollination limitations (e.g. flight distance of pollinators) most often restrict inter-population gene flow in insect pollinated species. In fragmented dry grasslands in northeastern Germany, we analysed genetic structure, fitness, and habitat quality of the endangered dioecious Silene otites (Caryophyllaceae). Using AFLP markers, a high level of differentiation among ten populations was found (F (st) = 0.36), while the intra-population genetic diversities (H (E) = 0.165-0.240) were similar as compared to hermaphroditic species. There was neither a correlation between geographic and genetic distance nor between genetic diversity and population size, which indicates reduced gene flow among populations and random genetic drift. Plant size was positively correlated with genetic diversity. Seed set and number of juveniles were positively related to population size. Higher total coverage resulted in reduced plant fitness, and the number of juveniles was negatively correlated to cryptogam cover. Additionally, we found a sex ratio bias towards more male plants in larger populations. Overall, our results indicate that on a regional geographic scale dioecy does not necessarily prevent genetic erosion in the case of habitat fragmentation, especially in the absence of long distance seed and pollen dispersal capacity.
The tricarboxylic acid (TCA) cycle is a crucial component of respiratory metabolism in both photosynthetic and heterotrophic plant organs. All of the major genes of the tomato TCA cycle have been cloned recently, allowing the generation of a suite of transgenic plants in which the majority of the enzymes in the pathway are progressively decreased. Investigations of these plants have provided an almost complete view of the distribution of control in this important pathway. Our studies suggest that citrate synthase, aconitase, isocitrate dehydrogenase, succinyl CoA ligase, succinate dehydrogenase, fumarase and malate dehydrogenase have control coefficients flux for respiration of -0.4, 0.964, -0.123, 0.0008, 0.289, 0.601 and 1.76, respectively; while 2-oxoglutarate dehydrogenase is estimated to have a control coefficient of 0.786 in potato tubers. These results thus indicate that the control of this pathway is distributed among malate dehydrogenase, aconitase, fumarase, succinate dehydrogenase and 2-oxoglutarate dehydrogenase. The unusual distribution of control estimated here is consistent with specific non-cyclic flux mode and cytosolic bypasses that operate in illuminated leaves. These observations are discussed in the context of known regulatory properties of the enzymes and some illustrative examples of how the pathway responds to environmental change are given.
Syntheses of thiazolidine-fused heterocycles via exo-mode cyclizations of vinylogous N-acyliminium ions incorporating heteroatom-based nucleophiles have been examined and discussed. The formation of (5,6)-membered systems was feasible with all nucleophiles tried (O, S and N), while the closing of the five-membered ring was restricted to O- and S-nucleophiles. The closure of a four-membered ring failed. Instead, the bicyclic (5,6)-membered acetal derivative and the tricyclic system with an eight-membered central ring were obtained from the substrates containing O and S nucleophilic moieties, respectively. The reaction outcome and stereochemistry are rationalized using quantum chemical calculations at B3LYP/6-31G(d) level. The exclusive cis-stereoselectivity in the formation of (5,6)- and (5,5)-membered systems results from thermodynamic control, whereas the formation of the eight-membered ring was kinetically controlled.
Global warming has created a need for studies along climatic gradients to assess the effects of temperature on ecological processes. Altitudinal and latitudinal gradients are often used as such, usually in combination with air temperature data from the closest weather station recorded at 1.52 m above the ground. However, many ecological processes occur in, at, or right above the soil surface. To evaluate how representative the commonly used weather station data are for the microclimate relevant for soil surface biota, we compared weather station temperatures for an altitudinal (500900 m a.s.l.) and a latitudinal gradient (4968 degrees N) with data obtained by temperature sensors placed right below the soil surface at five sites along these gradients. The mean annual temperatures obtained from weather stations and adjusted using a lapse rate of -5.5 degrees C km-1 were between 3.8 degrees C lower and 1.6 degrees C higher than those recorded by the temperature sensors at the soil surface, depending on the position along the gradients. The monthly mean temperatures were up to 10 degrees C warmer or 5 degrees C colder at the soil surface. The within-site variation in accumulated temperature was as high as would be expected from a 300 m change in altitude or from a 4 degrees change in latitude or a climate change scenario corresponding to warming of 1.63.8 degrees C. Thus, these differences introduced by the decoupling are significant from a climate change perspective, and the results demonstrate the need for incorporating microclimatic variation when conducting studies along altitudinal or latitudinal gradients. We emphasize the need for using relevant temperature data in climate impact studies and further call for more studies describing the soil surface microclimate, which is crucial for much of the biota.
Objectives-The purpose of this study was to determine the dependence of breast tissue elasticity on the menstrual cycle of healthy volunteers by means of real-time sonoelastography.
Methods-Twenty-two healthy volunteers (aged 18-33 years) were examined once weekly during two consecutive menstrual cycles using sonoelastography. Group 1 (n = 10) was not taking hormonal medication; group 2 (n = 12) was taking oral contraceptives.
Results-The breast parenchyma appeared softer than the dermis and harder than the adipose tissue, and elasticity varied over the menstrual cycle and between groups. Group 1 (no hormone intake) showed continuously increasing elasticity with relatively soft breast parenchyma in the menstrual and follicular phases and harder parenchyma in the luteal phase (P = .012). Group 2 (oral contraceptives) showed no statistically significant changes in breast parenchymal elasticity according to sonoelastography. The parenchyma was generally softer in group 1 compared with group 2 throughout the menstrual cycle (P = .033). The dermis, the subcutaneous adipose tissue, and the pectoralis major muscle showed no changes in elasticity. Comparison of measurements made during the first and the second menstrual cycles showed similar patterns of elasticity in both groups.
Conclusions-Sonoelastography is a reproducible method that can be used to determine the dependence of breast parenchyma elasticity on the menstrual cycle and on the intake of hormonal contraceptives.
The rooted zone of a soil, more precisely the rhizosphere, is a very dynamic system. Some of the key processes are water uptake and root respiration. We have developed a novel method for measuring the real-time distribution of water and oxygen concentration in the rhizosphere as a biogeochemical interface in soil. This enables understanding where and when roots are active in respect to root respiration and water uptake and how the soil responds to it.
We used glass containers (15 x 15 x 1 cm), which were filled with a quartz sand mixture. Sensor foils for fluorescence dye imaging of O-2 were installed on the inner side of the containers. A lupine plant was grown in each container for 2 weeks under controlled conditions. Then we took time series of fluorescence images for time-lapsed visualization of oxygen depletion caused by root respiration. Changing water content was mapped in parallel by non-invasive neutron radiography, which yields water content distributions in high spatial resolution. Also it can detect the root system of the lupine plants. By this combined imaging of the samples, a range of water contents and different oxygen concentration levels, both induced by root activities, could be assessed.
We monitored the dynamics of these vital parameters induced by roots during a period of several hours. We observed that for high water saturation, the oxygen concentration decreased in parts of the container. The accompanying neutron radiographies gave us the information that these locations are spatially correlated to roots. Therefore, it can be concluded that the observed oxygen deficits close to the roots result from root respiration and show up while re-aeration from atmosphere by gas phase transport is restricted by the high water saturation.
Our coupled imaging setup was able to monitor the spatial distribution and temporal dynamics of oxygen and water content in a night and day cycle. This reflects complex plant activities such as photosynthesis, transpiration, and metabolic activities impacting the root-soil interface. Our experimental setup provides the possibility to non-invasively visualize these parameters with high resolution. The particular oxygen imaging method as well as the combination with simultaneously mapping the water content by neutron radiography is a novelty.
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.
Inspired by the results from the PISA study and based on previous intervention programs, the reading competence training LEKOLEMO (Program for Fostering Reading Literacy and Reading Motivation) for 7th-grade students was developed. The training differs from existing programs in two aspects: (1) It comprises tasks pertaining to the PISA reading dimensions retrieving information, text-related interpretation, and reflection and evaluation, and (2) explicitly aims at fostering reading motivation. The present study examined the revised version of LEKOLEMO in a sample of 235 seventh graders. The results confirmed the effectiveness of LEKOLEMO and showed significant effects of medium size on reading competence at the follow-up test. However, effects on intrinsic reading motivation and on self-concept of reading were small and unstable.
Currently used costing methods such as cost centre accounting do not sufficiently reflect the process-based resource utilization in medicine. The goal of this study was to establish a process-oriented cost assessment of percutaneous radiofrequency (RF) ablation of liver and lung metastases.
In each of 15 patients a detailed task analysis of the primary process of hepatic and pulmonary RF ablation was performed. Based on these data a dedicated cost calculation model was developed for each primary process. The costs of each process were computed and compared with the revenue for in-patients according to the German diagnosis-related groups (DRG) system 2010.
The RF ablation of liver metastases in patients without relevant comorbidities and a low patient complexity level results in a loss of EUR 588.44, whereas the treatment of patients with a higher complexity level yields an acceptable profit. The treatment of pulmonary metastases is profitable even in cases of additional expenses due to complications.
Process-oriented costing provides relevant information that is needed for understanding the economic impact of treatment decisions. It is well suited as a starting point for economically driven process optimization and reengineering. Under the terms of the German DRG 2010 system percutaneous RF ablation of lung metastases is economically reasonable, while RF ablation of liver metastases in cases of low patient complexity levels does not cover the costs.
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.