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Information about the strength of donor-acceptor interactions in push-pull alkenes is valuable, as this so-called "push-pull effect' influences their chemical reactivity and dynamic behaviour. In this paper, we discuss the applicability of NMR spectral data and barriers to rotation around the CQC double bond to quantify the push-pull effect in biologically important 2-alkylidene-4-oxothiazolidines. While olefinic proton chemical shifts and differences in C-13 NMR chemical shifts of the two carbons constituting the CQC double bond fail to give the correct trend in the electron withdrawing ability of the substituents attached to the exocyclic carbon of the double bond, barriers to rotation prove to be a reliable quantity in providing information about the extent of donor-acceptor interactions in the push-pull systems studied. In particular all relevant kinetic data, that is the Arrhenius parameters ( apparent activation energy Ea and frequency factor A) and activation parameters ( Delta S-double dagger, Delta H-double dagger and Delta G(double dagger)), were determined from the data of the experimentally studied configurational isomerization of ( E)-9a. These results were compared to previously published related data for other two compounds, ( Z)-1b and ( 2E, 5Z)-7, showing that experimentally determined Delta G(double dagger) values are a good indicator of the strength of push-pull character. Theoretical calculations of the rotational barriers of eight selected derivatives excellently correlate with the calculated CQC bond lengths and corroborate the applicability of Delta G(double dagger) for estimation of the strength of the push-pull effect in these and related systems.
In June 2013, widespread flooding and consequent damage and losses occurred in Central Europe, especially in Germany. This paper explores what data are available to investigate the adverse impacts of the event, what kind of information can be retrieved from these data and how well data and information fulfil requirements that were recently proposed for disaster reporting on the European and international levels. In accordance with the European Floods Directive (2007/60/EC), impacts on human health, economic activities (and assets), cultural heritage and the environment are described on the national and sub-national scale. Information from governmental reports is complemented by communications on traffic disruptions and surveys of flood-affected residents and companies.
Overall, the impacts of the flood event in 2013 were manifold. The study reveals that flood-affected residents suffered from a large range of impacts, among which mental health and supply problems were perceived more seriously than financial losses. The most frequent damage type among affected companies was business interruption. This demonstrates that the current scientific focus on direct (financial) damage is insufficient to describe the overall impacts and severity of flood events.
The case further demonstrates that procedures and standards for impact data collection in Germany are widely missing. Present impact data in Germany are fragmentary, heterogeneous, incomplete and difficult to access. In order to fulfil, for example, the monitoring and reporting requirements of the Sendai Framework for Disaster Risk Reduction 2015-2030 that was adopted in March 2015 in Sendai, Japan, more efforts on impact data collection are needed.
Climate science today makes use of a variety of red globes to explore and communicate findings. These transform the iconography which informs this image: the idealised, even mythical vision of the blue, vulnerable and perfect marble is impaired by the application of the colours yellow and red. Since only predictions that employ a lot of red seem to exist, spectators are confronted with the message that the future Earth that might turn out as envisaged here is undesirable. Here intuitively powerful narrations of the end of the world may connect. By employing methods of art history and visual analysis, and building on examples from current Intergovernmental Panel on Climate Change reports and future scenario maps, this article explores how burning world images bear - intentionally or not - elements of horror and shock. My question explored here is as follows: should 'burning world' images be understood as a new and powerful cosmology?
The Paleocene was a time of transition for the Arctic, with magmatic activity of the High Arctic Large Igneous Province (HALIP) giving way to magmatism of the North Atlantic Large Igneous Province in connection to plate tectonic changes in the Arctic and North Atlantic. In this study we investigate the Paleocene magmatic record and sediment pathways of the Basilika Formation exposed in the Central Tertiary Basin of Svalbard. By means of geochemistry, SmNd isotopic signatures, and zircon UPb geochronology we investigate the characteristics of several bentonite layers contained in the Basilika Formation, as well as the provenance of the intercalated clastic sediments. Our data show that the volcanic ash layers of the Basilika Formation, which were diagenetically altered to bentonites, originate from alkaline continental-rift magmatism such as the last, explosive stages of the HALIP in North Greenland and the Canadian Arctic. The volcanic ash layers were deposited on Svalbard in a flat shelf environment with dominant sediment supply from the east. Dating of detrital zircons suggests that the detritus was derived from Siberian sources, primarily from the Verkhoyansk Fold-and-Thrust Belt, which would require transport over similar to 3000 km across the Arctic.
Low Earth orbiting geomagnetic satellite missions, such as the Swarm satellite mission, are the only means to monitor and investigate ionospheric currents on a global scale and to make in situ measurements of F region currents. High-precision geomagnetic satellite missions are also able to detect ionospheric currents during quiet-time geomagnetic conditions that only have few nanotesla amplitudes in the magnetic field. An efficient method to isolate the ionospheric signals from satellite magnetic field measurements has been the use of residuals between the observations and predictions from empirical geomagnetic models for other geomagnetic sources, such as the core and lithospheric field or signals from the quiet-time magnetospheric currents. This study aims at highlighting the importance of high-resolution magnetic field models that are able to predict the lithospheric field and that consider the quiet-time magnetosphere for reliably isolating signatures from ionospheric currents during geomagnetically quiet times. The effects on the detection of ionospheric currents arising from neglecting the lithospheric and magnetospheric sources are discussed on the example of four Swarm orbits during very quiet times. The respective orbits show a broad range of typical scenarios, such as strong and weak ionospheric signal (during day- and nighttime, respectively) superimposed over strong and weak lithospheric signals. If predictions from the lithosphere or magnetosphere are not properly considered, the amplitude of the ionospheric currents, such as the midlatitude Sq currents or the equatorial electrojet (EEJ), is modulated by 10-15 % in the examples shown. An analysis from several orbits above the African sector, where the lithospheric field is significant, showed that the peak value of the signatures of the EEJ is in error by 5 % in average when lithospheric contributions are not considered, which is in the range of uncertainties of present empirical models of the EEJ.
Encapsulation of diagnostic and therapeutic compounds in transporters improves their delivery to the point of need. An even more efficient treatment of diseases can be achieved using carriers with targeting or protecting moieties. In the present work, we investigated micellar and liposomal nanocarriers modified with fluorescein, peptides, and polymers that are covalently bound to fatty acids or phospholipids to ensure a self-driven incorporation into the micelles or liposomes. First, we characterized the photophysics of the fluorescent probes in the absence and in the presence of nanocarriers. Changes in the fluorescence decay time, quantum yield, and intensity of a fluorescein-labeled fatty acid (fluorescein-labeled palmitic acid [fPA]) and a fluorescein-labeled lipopeptide (P2fA2) were found. By exploiting these changes, we investigated a lipopeptide (P2A2 as an uptake-mediating unit) in combination with different nanocarriers (micelles and liposomes) and determined the corresponding association constant K-ass values, which were found to be very high. In addition, the mobility of fPA was exploited using fluorescence correlation spectroscopy (FCS) and fluorescence depolarization (FD) experiments to characterize the nanocarriers. Cellular uptake experiments with mouse brain endothelial cells provided information on the uptake behavior of liposomes modified by uptake-mediating P2A2 and revealed differences in the uptake behavior between pH-sensitive and pH-insensitive liposomes.
We study the modeling and prediction of dynamical systems based on conventional models derived from measurements. Such algorithms are highly desirable in situations where the underlying dynamics are hard to model from physical principles or simplified models need to be found. We focus on symbolic regression methods as a part of machine learning. These algorithms are capable of learning an analytically tractable model from data, a highly valuable property. Symbolic regression methods can be considered as generalized regression methods. We investigate two particular algorithms, the so-called fast function extraction which is a generalized linear regression algorithm, and genetic programming which is a very general method. Both are able to combine functions in a certain way such that a good model for the prediction of the temporal evolution of a dynamical system can be identified. We illustrate the algorithms by finding a prediction for the evolution of a harmonic oscillator based on measurements, by detecting an arriving front in an excitable system, and as a real-world application, the prediction of solar power production based on energy production observations at a given site together with the weather forecast.
Antibodies against spike proteins of influenza are used as a tool for characterization of viruses and therapeutic approaches. However, development, production and quality control of antibodies is expensive and time consuming. To circumvent these difficulties, three peptides were derived from complementarity determining regions of an antibody heavy chain against influenza A spike glycoprotein. Their binding properties were studied experimentally, and by molecular dynamics simulations. Two peptide candidates showed binding to influenza A/Aichi/2/68 H3N2. One of them, termed PeB, with the highest affinity prevented binding to and infection of target cells in the micromolar region without any cytotoxic effect. PeB matches best the conserved receptor binding site of hemagglutinin. PeB bound also to other medical relevant influenza strains, such as human-pathogenic A/California/7/2009 H1N1, and avian-pathogenic A/MuteSwan/Rostock/R901/2006 H7N1. Strategies to improve the affinity and to adapt specificity are discussed and exemplified by a double amino acid substituted peptide, obtained by substitutional analysis. The peptides and their derivatives are of great potential for drug development as well as biosensing.
Earthworms play a key role in regulating soil ecosystem functions and services. The small scale variability in earthworm abundance is often found to be very high, which is a problem for representative sampling of earthworm abundance at larger scales. In agricultural fields, soil tillage may influence both the average earthworm abundance as well as the spatial distribution of earthworms. Therefore we studied the abundance and spatial pattern of the different ecological earthworm types, i.e. endogeic, epigeic and anecic earthworms, in four agricultural fields differing in soil tillage (two fields with regular tillage and two fields with conservation tillage) and surrounding land use (other cropped fields or apple orchard and forest). To this aim we sampled earthworms on a total number of 430 plots (50 x 50 cm(2)) using a combination of extraction with mustard solution and hand sorting. The results exhibit large differences in average earthworm abundance between the four fields. Only one of the two fields with conservation tillage had a comparatively very high overall abundance of earthworms. Furthermore, we found a high spatial variability of earthworms within the field scale often exhibiting a patchy distribution. We detected a trend of decreasing earthworm abundances from the field border into the field for different earthworm groups on each of the fields. In three fields with low total earthworm abundance (and only very few epigeic earthworms) there was a short scale autocorrelation with ranges varying strongly for the endogeic earthworms (37.9 m, 62.6 m, and 85.2 m) compared to anecic earthworms (19.8 m, 22.8 m, and 27.4 m). In the field with high abundance, after trend removal, the variogram models for anecic and endogeic earthworms were rejected based on their negative explained variances. On this field, we found only a short scale autocorrelation for the epigeic earthworms with a range of 143 m. Based on these results it seems that ploughing alone cannot explain the differences in abundance and range of autocorrelation found on the four fields. The trend of strongly decreasing earthworm abundance from the field border into the field in the one field with high abundance does indicate that the field border or surrounding land use may also influence the recolonization of fields, but more research is required to provide further evidence for this hypothesis. Due to the very different patterns of earthworm distributions in the fields it remains difficult to recommend an optimal number and distance of samples to obtain a representative earthworm abundance for the field scale. (C) 2016 Elsevier B.V. All rights reserved.
In this study, we investigated the scale sizes of equatorial plasma irregularities (EPIs) using measurements from the Swarm satellites during its early mission and final constellation phases. We found that with longitudinal separation between Swarm satellites larger than 0.4 degrees, no significant correlation was found any more. This result suggests that EPI structures include plasma density scale sizes less than 44 km in the zonal direction. During the Swarm earlier mission phase, clearly better EPI correlations are obtained in the northern hemisphere, implying more fragmented irregularities in the southern hemisphere where the ambient magnetic field is low. The previously reported inverted-C shell structure of EPIs is generally confirmed by the Swarm observations in the northern hemisphere, but with various tilt angles. From the Swarm spacecrafts with zonal separations of about 150 km, we conclude that larger zonal scale sizes of irregularities exist during the early evening hours (around 1900 LT).
The recognition and understanding of vegetated habitats in the fossil record are of crucial importance in order to investigate paleoecological responses and indirectly infer climate and sea-level changes. However, the low preservation potential of plants and macroalgae hampers a direct identification of these environments in the geological past. Here we present sedimentological and paleontological evidences as tool to identify the presence of different seagrass-vegetated environments in the shallow marine settings of the lower Eocene jafnayn platform of Oman and their responses to paleoenvironmental changes. The studied lower Eocene deposits consist of well bedded, nodular pacicstones dominated by encrusting acervulinid and alveolinid foraminifera passing upward to an alternance of packstones with echinoids and quartz grains and grainstones rich in Orbitolites, smaller miliolid foraminifera and quartz grains. The presence of seagrass is inferred by the occurrence of encrusting acervulinids and soritid Orbitolites, as well as by their test morphologies together with further sedimentological criteria. The clear shift observed in the faunal assemblages and sedimentary features may be related to a major reorganization of the carbonate system passing from a carbonate platform to a ramp-like platform with increased terrigenous sedimentation. Heterotroph tubular acervulinids and oligotroph alveolinids of the carbonate platform were replaced upward by more heterotroph organisms such as large, discoidal Orbitolites and smaller miliolids, most likely due to enhanced nutrient levels which would have led to a change of phytal substrate, from cylindrical-leaf dominated grasses into flat-leafed ones. (C) 2016 Elsevier B.V. All rights reserved.
The Eukaryotic-Specific ISD11 Is a Complex-Orphan Protein with Ability to Bind the Prokaryotic IscS
(2016)
The eukaryotic protein Isd11 is a chaperone that binds and stabilizes the central component of the essential metabolic pathway responsible for formation of iron-sulfur clusters in mitochondria, the desulfurase Nfs1. Little is known about the exact role of Isd11. Here, we show that human Isd11 (ISD11) is a helical protein which exists in solution as an equilibrium between monomer, dimeric and tetrameric species when in the absence of human Nfs1 (NFS1). We also show that, surprisingly, recombinant ISD11 expressed in E. coli co-purifies with the bacterial orthologue of NFS1, IscS. Binding is weak but specific suggesting that, despite the absence of Isd11 sequences in bacteria, there is enough conservation between the two desulfurases to retain a similar mode of interaction. This knowledge may inform us on the conservation of the mode of binding of Isd11 to the desulfurase. We used evolutionary evidence to suggest Isd11 residues involved in the interaction.
Volunteered geographical information (VGI) and citizen science have become important sources data for much scientific research. In the domain of land cover, crowdsourcing can provide a high temporal resolution data to support different analyses of landscape processes. However, the scientists may have little control over what gets recorded by the crowd, providing a potential source of error and uncertainty. This study compared analyses of crowdsourced land cover data that were contributed by different groups, based on nationality (labelled Gondor and Non-Gondor) and on domain experience (labelled Expert and Non-Expert). The analyses used a geographically weighted model to generate maps of land cover and compared the maps generated by the different groups. The results highlight the differences between the maps how specific land cover classes were under-and over-estimated. As crowdsourced data and citizen science are increasingly used to replace data collected under the designed experiment, this paper highlights the importance of considering between group variations and their impacts on the results of analyses. Critically, differences in the way that landscape features are conceptualised by different groups of contributors need to be considered when using crowdsourced data in formal scientific analyses. The discussion considers the potential for variation in crowdsourced data, the relativist nature of land cover and suggests a number of areas for future research. The key finding is that the veracity of citizen science data is not the critical issue per se. Rather, it is important to consider the impacts of differences in the semantics, affordances and functions associated with landscape features held by different groups of crowdsourced data contributors.
Background: Gestational diabetes mellitus (GDM) is associated with adverse pregnancy outcomes. It is known that GDM is associated with an altered placental function and changes in placental gene regulation. More recent studies demonstrated an involvement of epigenetic mechanisms. So far, the focus regarding placental epigenetic changes in GDM was set on gene-specific DNA methylation analyses. Studies that robustly investigated placental global DNA methylation are lacking. However, several studies showed that tissue-specific alterations in global DNA methylation are independently associated with type 2 diabetes. Thus, the aim of this study was to characterize global placental DNA methylation by robustly measuring placental DNA 5-methylcytosine (5mC) content and to examine whether differences in placental global DNA methylation are associated with GDM. Methods: Global DNA methylation was quantified by the current gold standard method, LC-MS/MS. In total, 1030 placental samples were analyzed in this single-center birth cohort study. Results: Mothers with GDM displayed a significantly increased global placental DNA methylation (3.22 +/- 0.63 vs. 3.00 +/- 0.46 %; p = 0.013; +/- SD). Bivariate logistic regression showed a highly significant positive correlation between global placental DNA methylation and the presence of GDM (p = 0.0009). Quintile stratification according to placental DNA 5mC levels revealed that the frequency of GDM was evenly distributed in quintiles 1-4 (2.9-5.3 %), whereas the frequency in the fifth quintile was significantly higher (10.7 %; p = 0.003). Bivariate logistic models adjusted for maternal age, BMI, ethnicity, recurrent miscarriages, and familiar diabetes predisposition clearly demonstrated an independent association between global placental DNA hypermethylation and GDM. Furthermore, an ANCOVA model considering known predictors of DNA methylation substantiated an independent association between GDM and placental DNA methylation. Conclusions: This is the first study that employed a robust quantitative assessment of placental global DNA methylation in over a thousand placental samples. The study provides large scale evidence that placental global DNA hypermethylation is associated with GDM, independent of established risk factors.
Surface-enhanced infrared absorption spectroscopy (SEIRA) is applied to study protein conformational changes. In general, the appropriate functionalization of metal surfaces with biomolecules remains a challenge if the conformation and activity of the biomolecule shall be preserved. Here we present a SEIRA study to monitor pH-induced conformational changes of poly-L lysine (PLL) covalently bound to a thin gold layer via self assembled monolayers (SAMs). We demonstrate that the composition of the SAM is crucial. A SAM of 11-mercaptoundecanonic acid (MUA) can link PLL to the gold layer, but pH-driven conformational transitions were hindered compared to poly-L lysine in solution. To address this problem, we devised a variety of SAMs, i.e., mixed SAMs of MUA with either octanethiol (OT) or 11-mercapto-1-undecanol (MUoL) and furthermore SAMs of MT(PEG)(4) and NHS-PEG(10k)-SH. These mixed SAMs modify the surface properties by changing the polarity and the morphology of the surface present to nearby PLL molecules. Our experiments reveal that mixed SAMs of MUA-MUoL and SAMs of NHS-PEG(10k)-SH-MT(PEG)(4) are suitable to monitor pH-driven conformational changes of immobilized PLL. These SAMs might be applicable for chemoselective protein immobilization in general.
Underdamped scaled Brownian motion: (non-)existence of the overdamped limit in anomalous diffusion
(2016)
It is quite generally assumed that the overdamped Langevin equation provides a quantitative description of the dynamics of a classical Brownian particle in the long time limit. We establish and investigate a paradigm anomalous diffusion process governed by an underdamped Langevin equation with an explicit time dependence of the system temperature and thus the diffusion and damping coefficients. We show that for this underdamped scaled Brownian motion (UDSBM) the overdamped limit fails to describe the long time behaviour of the system and may practically even not exist at all for a certain range of the parameter values. Thus persistent inertial effects play a non-negligible role even at significantly long times. From this study a general questions on the applicability of the overdamped limit to describe the long time motion of an anomalously diffusing particle arises, with profound consequences for the relevance of overdamped anomalous diffusion models. We elucidate our results in view of analytical and simulations results for the anomalous diffusion of particles in free cooling granular gases.
We investigate light-induced changes in thickness and roughness of photosensitive polymer brushes containing azobenzene cationic surfactants by atomic force microscopy (AFM) in real time during light irradiation. Because the cis-state of azobenzene unit requires more free volume than its trans counterpart, the UV light-induced expansion of polymer thin films associated with the trans-to-cis isomerism of azobenzene groups is expected to occur. This phenomenon is well documented in physisorbed polymer films containing azobenzene groups. In contrast, photosensitive polymer brushes show a decrease in thickness under UV irradiation. We have found that the azobenzene surfactants in their trans-state form aggregates within the brush. Under irradiation, the surfactants undergo photoisomerization to the cis-state, which is more hydrophilic. As a consequence, the aggregates within the brush are disrupted, and the polymer brush contracts. When subsequently irradiated with blue light the polymer brush thickness returns back to its initial value. This behavior is related to isomerization of the surfactant to the more hydrophobic trans-state and subsequent formation of surfactant aggregates within the polymer brush. The photomechanical function of the dry polymer brush, i.e., contraction and expansion, was found to be reversible with repeated irradiation cycles and requires only a few seconds for switching. In addition to the thickness change, the roughness of the brush also changes reversibly between a few Angstroms (blue light) and several nanometers (UV light). Photosensitive polymer brushes represent smart films with light responsive thickness and roughness that could be used for generating dynamic fluctuating surfaces, the function of which can be turned on and off in a controllable manner on a nanometer length scale.
Understanding interactions of bacterial surface polysaccharides with receptor protein scaffolds is important for the development of antibiotic therapies. The corresponding protein recognition domains frequently form low-affinity complexes with polysaccharides that are difficult to address with experimental techniques due to the conformational flexibility of the polysaccharide. In this work, we studied the tailspike protein (TSP) of the bacteriophage Sf6. Sf6TSP binds and hydrolyzes the high-rhamnose, serotype Y O-antigen polysaccharide of the Gram-negative bacterium Shigella flexneri (S. flexneri) as a first step of bacteriophage infection. Spectroscopic analyses and enzymatic cleavage assays confirmed that Sf6TSP binds long stretches of this polysaccharide. Crystal structure analysis and saturation transfer difference (STD) NMR spectroscopy using an enhanced method to interpret the data permitted the detailed description of affinity contributions and flexibility in an Sf6TSP-octasaccharide complex. Dodecasaccharide fragments corresponding to three repeating units of the O-antigen in complex with Sf6TSP were studied computationally by molecular dynamics simulations. They showed that distortion away from the low-energy solution conformation found in the octasaccharide complex is necessary for ligand binding. This is in agreement with a weak-affinity functional polysaccharide protein contact that facilitates correct placement and thus hydrolysis of the polysaccharide close to the catalytic residues. Our simulations stress that the flexibility of glycan epitopes together with a small number of specific protein contacts provide the driving force for Sf6TSP-polysaccharide complex formation in an overall weak-affinity interaction system.
The optical properties of semiconductor nanocrystals (SC NCs) are largely controlled by their size and surface chemistry, i.e., the chemical composition and thickness of inorganic passivation shells and the chemical nature and number of surface ligands as well as the strength of their bonds to surface atoms. The latter is particularly important for CdTe NCs, which – together with alloyed CdxHg1−xTe – are the only SC NCs that can be prepared in water in high quality without the need for an additional inorganic passivation shell. Aiming at a better understanding of the role of stabilizing ligands for the control of the application-relevant fluorescence features of SC NCs, we assessed the influence of two of the most commonly used monodentate thiol ligands, thioglycolic acid (TGA) and mercaptopropionic acid (MPA), on the colloidal stability, photoluminescence (PL) quantum yield (QY), and PL decay behavior of a set of CdTe NC colloids. As an indirect measure for the strength of the coordinative bond of the ligands to SC NC surface atoms, the influence of the pH (pD) and the concentration on the PL properties of these colloids was examined in water and D2O and compared to the results from previous dilution studies with a set of thiol-capped Cd1−xHgxTe SC NCs in D2O. As a prerequisite for these studies, the number of surface ligands was determined photometrically at different steps of purification after SC NC synthesis with Ellman's test. Our results demonstrate ligand control of the pH-dependent PL of these SC NCs, with MPA-stabilized CdTe NCs being less prone to luminescence quenching than TGA-capped ones. For both types of CdTe colloids, ligand desorption is more pronounced in H2O compared to D2O, underlining also the role of hydrogen bonding and solvent molecules.