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Institute
- Institut für Biochemie und Biologie (232)
- Institut für Geowissenschaften (211)
- Institut für Physik und Astronomie (181)
- Institut für Chemie (165)
- Department Psychologie (69)
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XopJ is a Xanthomonas type III effector protein that promotes bacterial virulence on susceptible pepper plants through the inhibition of the host cell proteasome and a resultant suppression of salicylic acid (SA) - dependent defense responses. We show here that Nicotiana benthamiana leaves transiently expressing XopJ display hypersensitive response (HR) -like symptoms when exogenously treated with SA. This apparent avirulence function of XopJ was further dependent on effector myristoylation as well as on an intact catalytic triad, suggesting a requirement of its enzymatic activity for HR-like symptom elicitation. The ability of XopJ to cause a HR-like symptom development upon SA treatment was lost upon silencing of SGT1 and NDR1, respectively, but was independent of EDS1 silencing, suggesting that XopJ is recognized by an R protein of the CC-NBS-LRR class. Furthermore, silencing of NPR1 abolished the elicitation of HR-like symptoms in XopJ expressing leaves after SA application. Measurement of the proteasome activity indicated that proteasome inhibition by XopJ was alleviated in the presence of SA, an effect that was not observed in NPR1 silenced plants. Our results suggest that XopJ - triggered HR-like symptoms are closely related to the virulence function of the effector and that XopJ follows a two-signal model in order to elicit a response in the non-host plant N. benthamiana.
The application of electrospray ionization (ESI) ion mobility (IM) spectrometry on the detection end of a high-performance liquid chromatograph has been a subject of study for some time. So far, this method has been limited to low flow rates or has required splitting of the liquid flow. This work presents a novel concept of an ESI source facilitating the stable operation of the spectrometer at flow rates between 10 mu L min(-1) and 1500 mu L min(-1) without flow splitting, advancing the T-cylinder design developed by Kurnin and co-workers. Flow rates eight times faster than previously reported were achieved because of a more efficient dispersion of the liquid at increased electrospray voltages combined with nebulization by a sheath gas. Imaging revealed the spray operation to be in a rotationally symmetric multijet-mode. The novel ESI-IM spectrometer tolerates high water contents (<= 90%) and electrolyte concentrations up to 10 mM, meeting another condition required of high-performance liquid chromatography (HPLC) detectors. Limits of detection of 50 nM for promazine in the positive mode and 1 mu M for 1,3-dinitrobenzene in the negative mode were established. Three mixtures of reduced complexity (five surfactants, four neuroleptics, and two isomers) were separated in the millisecond regime in stand-alone operation of the spectrometer. Separations of two more complex mixtures (five neuroleptics and 13 pesticides) demonstrate the application of the spectrometer as an HPLC detector. The examples illustrate the advantages of the spectrometer over the established diode array detector, in terms of additional IM separation of substances not fully separated in the retention time domain as well as identification of substances based on their characteristic IMs.
Density regulation influences population dynamics through its effects on demographic rates and consequently constitutes a key mechanism explaining the response of organisms to environmental changes. Yet, it is difficult to establish the exact form of density dependence from empirical data. Here, we developed an individual-based model to explore how resource limitation and behavioural processes determine the spatial structure of white stork Ciconia ciconia populations and regulate reproductive rates. We found that the form of density dependence differed considerably between landscapes with the same overall resource availability and between home range selection strategies, highlighting the importance of fine-scale resource distribution in interaction with behaviour. In accordance with theories of density dependence, breeding output generally decreased with density but this effect was highly variable and strongly affected by optimal foraging strategy, resource detection probability and colonial behaviour. Moreover, our results uncovered an overlooked consequence of density dependence by showing that high early nestling mortality in storks, assumed to be the outcome of harsh weather, may actually result from density dependent effects on food provision. Our findings emphasize that accounting for interactive effects of individual behaviour and local environmental factors is crucial for understanding density-dependent processes within spatially structured populations. Enhanced understanding of the ways animal populations are regulated in general, and how habitat conditions and behaviour may dictate spatial population structure and demographic rates is critically needed for predicting the dynamics of populations, communities and ecosystems under changing environmental conditions.
This article presents a simple and facile method to fabricate thermoresponsive polymer-grafted silica particles by direct surface-initiated photopolymerization of N-isopropylacrylamide (NIPAM). This method is based on silica particles bearing thiol functionalities, which are transformed into thiyl radicals by irradiation with UV light to initiate the polymerization of NIPAM in aqueous media at room temperature. The photopolymerization of NIPAM could be applied to smaller thiol-functionalized particles (approximate to 48 nm) as well as to larger particles (approximate to 692 nm). Hollow poly(NIPAM) capsules could be formed after etching away the silica cores from the composite particles. It is possible to produce tailor-made composite particles or capsules for particular applications by extending this approach to other vinyl monomers. (c) 2015 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 2015, 53, 1260-1267
CXCL12-CXCR4 signaling controls multiple physiological processes and its dysregulation is associated with cancers and inflammatory diseases. To discover as-yet-unknown endogenous ligands of CXCR4, we screened a blood-derived peptide library for inhibitors of CXCR4-tropic HIV-1 strains. This approach identified a 16 amino acid fragment of serum albumin as an effective and highly specific CXCR4 antagonist. The endogenous peptide, termed EPI-X4, is evolutionarily conserved and generated from the highly abundant albumin precursor by pH-regulated proteases. EPI-X4 forms an unusual lasso-like structure and antagonizes CXCL12-induced tumor cell migration, mobilizes stem cells, and suppresses inflammatory responses in mice. Furthermore, the peptide is abundant in the urine of patients with inflammatory kidney diseases and may serve as a biomarker. Our results identify EPI-X4 as a key regulator of CXCR4 signaling and introduce proteolysis of an abundant precursor protein as an alternative concept for chemokine receptor regulation.
The article analyses whether the Palestinian-Israeli conflict has served as a catalyst for the development of international law, as well as whether international law has been instrumental in attempting to find solutions for the said conflict.
In several ways, this conflict has made a significant contribution to understanding and interpreting the UN Charter. It also brought along important developments about the role of third parties, both under the Geneva Conventions and under the law of state responsibility, which provides for an obligation of not recognizing as legal, or not rendering aid or assistance to situations caused by serious violations of jus cogens.
International judicial institutions (and also domestic ones) play a rather limited role in this respect, due both to a lack of courage to address fundamental questions, and/or a disregard of the outcome of the proceedings by at least one of the parties to the conflict. Other reasons are Israel's reluctance of accepting the jurisdiction of either the ICJ or the ICC, and its view on the non-applicability of human rights treaties outside of its territory, as well as Palestine's uncertain status in the international community limiting its access to international courts. However, the ICJ's 2004 (formally non-binding) advisory opinion on the Israeli Wall provided answers to some of the most fundamental questions related to the conflict, unfortunately without having any immediate impact on the situation on the ground. Given Palestine's accession to the Rome Statute in early 2015, time has yet to show which role in the process will be played by the ICC.
Other issues arising from the conflict, and examined by this article, are that of (Palestinian) statehood, going beyond the traditional concept of statehood and including the consequences of the jus cogens-character of the right of self-determination, as well as questions of treaty succession and succession in matters of State responsibility with regard to acts committed by the PLO.
Numerous studies investigated the influence of abiotic (meteorological conditions) and biotic factors (tree characteristics) on stemflow generation. Although these studies identified the variables that influence stemflow volumes in simply structured forests, the combination of tree characteristics that allows a robust prediction of stemflow volumes in species-rich forests is not well known. Many hydrological applications, however, require at least a rough estimate of stemflow volumes based on the characteristics of a forest stand. The need for robust predictions of stemflow motivated us to investigate the relationships between tree characteristics and stemflow volumes in a species-rich tropical forest located in central Panama. Based on a sampling setup consisting of ten rainfall collectors, 300 throughfall samplers and 60 stemflow collectors and cumulated data comprising 26 rain events, we derive three main findings. Firstly, stemflow represents a minor hydrological component in the studied 1-ha forest patch (1.0% of cumulated rainfall). Secondly, in the studied species-rich forest, single tree characteristics are only weakly related to stemflow volumes. The influence of multiple tree parameters (e.g. crown diameter, presence of large epiphytes and inclination of branches) and the dependencies among these parameters require a multivariate approach to understand the generation of stemflow. Thirdly, predicting stemflow in species-rich forests based on tree parameters is a difficult task. Although our best model can capture the variation in stemflow to some degree, a critical validation reveals that the model cannot provide robust predictions of stemflow. A reanalysis of data from previous studies in species-rich forests corroborates this finding. Based on these results and considering that for most hydrological applications, stemflow is only one parameter among others to estimate, we advocate using the base model, i.e. the mean of the stemflow data, to quantify stemflow volumes for a given study area. Studies in species-rich forests that wish to obtain predictions of stemflow based on tree parameters probably need to conduct a much more extensive sampling than currently implemented by most studies. Copyright (c) 2015 John Wiley & Sons, Ltd.
On 27 December 2007, a 1.9 seismic event occurred within a dyke in the deep-level Mponeng Gold Mine, South Africa. From the seismological network of the mine and the one from the Japanese-German Underground Acoustic Emission Research in South Africa (JAGUARS) group, the hypocentral depth (3,509 m), focal mechanism and aftershock location were estimated. Since no mining activity took place in the days before the event, dynamic triggering due to blasting can be ruled out as the cause. To investigate the hypothesis that stress transfer, due to excavation of the gold reef, induced the event, we set up a small-scale high-resolution three-dimensional (3D) geomechanical numerical model. The model consisted of the four different rock units present in the mine: quartzite (footwall), hard lava (hanging wall), conglomerate (gold reef) and diorite (dykes). The numerical solution was computed using a finite-element method with a discretised mesh of approximately elements. The initial stress state of the model is in agreement with in situ data from a neighbouring mine, and the step-wise excavation was simulated by mass removal from the gold reef. The resulting 3D stress tensor and its changes due to mining were analysed based on the Coulomb failure stress changes on the fault plane of the event. The results show that the seismic event was induced regardless of how the Coulomb failure stress changes were calculated and of the uncertainties in the fault plane solution. We also used the model to assess the seismic hazard due to the excavation towards the dyke. The resulting curve of stress changes shows a significant increase in the last in front of the dyke, indicating that small changes in the mining progress towards the dyke have a substantial impact on the stress transfer.
Camellia sinensis synthesizes and emits a large variety of volatile phenylpropanoids and benzenoids (VPB). To investigate the enzymes involved in the formation of these VPB compounds, a new C. sinensis short-chain dehydrogenase/reductase (CsSDR) was isolated, cloned, sequenced, and functionally characterized. The complete open reading frame of CsSDR contains 996 nucleotides with a calculated protein molecular mass of 34.5 kDa. The CsSDR recombinant protein produced in Escherichia coli exhibited dehydrogenase-reductase activity towards several major VPB compounds in C. sinensis flowers with a strong preference for NADP/NADPH co-factors, and showed affinity for (R)/(S)-1-phenylethanol (1PE), phenylacetaldehyde, benzaldehyde, and benzyl alcohol, and no affinity for acetophenone (AP) and 2-phenylethanol. CsSDR showed the highest catalytic efficiency towards (R)/(S)-1PE. Furthermore, the transient expression analysis in Nicotiana benthamiana plants validated that CsSDR could convert 1PE to AP in plants. CsSDR transcript level was not significantly affected by floral development and some jasmonic acid-related environmental stress, and CsSDR transcript accumulation was detected in most floral tissues such as receptacle and anther, which were main storage locations of VPB compounds. Our results indicate that CsSDR is expressed in C. sinensis flowers and is likely to contribute to a number of floral VPB compounds including the 1PE derivative AP.
Barite concretions and bands are widely distributed in black shale-chert horizons in the Yurtus Formation of Lower Cambrian in Aksu area, northwestern Tarim Basin, NW China. They mainly consist of coarse-grained anhedral to euhedral barite crystals with minor dolomites and pyrites. Petrological features indicate these concretions grew from the porewater in unconsolidated sediments at shallow burial below sediment-water interface. The slight deviation of Sr-87/Sr-86 ratios (0.7083 to 0.7090) and significant elevated delta S-34 values (56.8-76.4 parts per thousand CDT) of barite samples with respect to those of the Early Cambrian seawater further support that barite deposits precipitated from the enclosed porewater in sediment column, which evolved from the penecontemporaneous seawater with weak interaction with the host fine-grained siliciclastic sediments and highly-depleted sulfate in response to prolonged strong bacterial sulfate reduction without necessary renewal. The abundant organic matters in the basal Yurtus Formation should have facilitated developing sulfate-depleted methanogenesis zone and sulfate-methane transition zone (SMTZ) slightly after deposition. Therefore, barite deposits in the Yurtus Formation most likely resulted from diagenetic barium cycling and persistently grew from the porewater in the static SMTZ with a low sedimentation rate in the Early Cambrian. In comparison with the distribution of sedimentary barites in geological records, we tentatively proposed that a transition in diagenetic barium cycling and associated mineralization may have occurred from the Precambrian to Cambrian periods; this scenario may be causally linked to the changes in marine ecology (the advent of mesozooplankton and associated faecal pellet) and geochemistry (the increase of seawater sulfate concentration). Thus, the occurrence of diagenetic barite deposits in the Yurtus Formation implies that diagenetic barium cycling and more effective scavenging of barium from CH4- and Ba-rich porewaters within sediments might have become an nonnegligible process in continental margin areas, at least, since the earliest Cambrian, which could have significantly impacted the marine barium cycling. (C) 2015 Elsevier B.V. All rights reserved.
The rehydration of thermoresponsive poly(monomethoxydiethylene glycol acrylate) (PMDEGA) films exhibiting a lower critical solution temperature (LCST) type demixing phase transition in aqueous environments, induced by a decrease in temperature, is investigated in situ with real-time neutron reflectivity. Two different starting conditions (collapsed versus partially swollen chain conformation) are compared. In one experiment, the temperature is reduced from above the demixing temperature to well below the demixing temperature. In a second experiment, the starting temperature is below the demixing temperature, but within the transition regime, and reduced to the same final temperature. In both cases, the observed rehydration process can be divided into three stages: first condensation of water from the surrounding atmosphere, then absorption of water by the PMDEGA film and evaporation of excess water, and finally, rearrangement of the PMDEGA chains. The final rehydrated film is thicker and contains more absorbed water as compared with the initially swollen film at the same temperature well below the demixing temperature.
The Upper Cambrian Lower Qiulitag Group in the Tarim Basin, NW China, is overwhelmingly composed of cyclic dolomites. Based on extensive field investigations and facies analysis from four outcrop sections in the Bachu-Keping area, northwestern Tarim Basin, four main types of facies are recognized: open-marine subtidal, restricted shallow subtidal, intertidal, and supratidal facies, and these are further subdivided into ten lithofacies. In general, these facies are vertically arranged into shallowing-upward, metre-scale cycles. These cycles are commonly composed of a thin basal horizon reflecting abrupt deepening, and a thicker upper succession showing gradual shallowing upwards. Based on the vertical facies arrangements and changes across boundary surfaces, two types of cycle: peritidal and shallow subtidal cycle, are further identified. The peritidal cycles, predominating over the lower-middle Lower Qiulitag Group, commence with shallow subtidal to lower intertidal facies and are capped by inter-supratidal facies. In contrast, the shallow subtidal cycles, dominating the upper Lower Qiulitag Group, are capped by shallow-subtidal facies. Based on vertical lithofacies variations, cycle stacking patterns, and accommodation variations revealed by Fischer plots, six larger-scale third-order depositional sequences (Sq1-Sq6) are recognized. These sequences generally consist of a lower transgressive and an upper regressive systems tract. The transgressive tracts are dominated by thicker-than-average cycles, indicating an overall accommodation increase, whereas the regressive tracts are characterized by thinner-than-average peritidal cycles, indicating an overall accommodation decrease. The sequence boundaries are characterized by transitional zones of stacked thinner-than-average cycles, rather than by a single surface. These sequences can further be grouped into lower-order sequence sets: the lower and upper sequence sets. The lower sequence set, including Sq1-Sq3, is characterized by peritidal facies-dominated sequences and a progressive decrease in accommodation space, indicating a longer-term fall in sea level. In contrast, the upper sequence set (Sq4-Sq6) is characterized by subtidal facies-dominated sequences and a progressive increase in accommodation space, indicating a longer-term rise in sea level.
Shape-Memory Capability of Copolyetheresterurethane Microparticles Prepared via Electrospraying
(2015)
Multifunctional thermo-responsive and degradable microparticles exhibiting a shapememory effect (SME) have attracted widespread interest in biomedicine as switchable delivery vehicles or microactuators. In this work almost spherical solid microparticles with an average diameter of 3.9 +/- 0.9 mm are prepared via electrospraying of a copolyetheresterurethane named PDC, which is composed of crystallizable oligo(p-dioxanone) (OPDO) hard and oligo(e-caprolactone) (OCL) switching segments. The PDC microparticles are programmed via compression at different pressures and their shapememory capability is explored by off-line and online heating experiments. When a low programming pressure of 0.2 MPa is applied a pronounced thermally-induced shape-memory effect is achieved with a shape recovery ratio about 80%, while a high programming pressure of 100 MPa resulted in a weak shape-memory performance. Finally, it is demonstrated that an array of PDC microparticles deposited on a polypropylene (PP) substrate can be successfully programmed into a smart temporary film, which disintegrates upon heating to 60 degrees C.
The retinitis pigmentosa 2 polypeptide (RP2) functions as a GTPase-activating protein (GAP) for ARL3 (Arf-like protein 3), a small GTPase. ARL3 is an effector of phosphodiesterase 6 Delta (PDE6D), a prenyl-binding protein and chaperone of prenylated protein in photoreceptors. Mutations in the human RP2 gene cause X-linked retinitis pigmentosa (XLRP) and cone-rod dystrophy (XL-CORD). To study mechanisms causing XLRP, we generated an RP2 knockout mouse. The RP2h(-/-) mice exhibited a slowly progressing rod-cone dystrophy simulating the human disease. RP2h(-/-) scotopic a-wave and photopic b-wave amplitudes declined at 1 mo of age and continued to decline over the next 6 mo. Prenylated PDE6 subunits and G-protein coupled receptor kinase 1 (GRK1) were unable to traffic effectively to the RP2h(-/-) outer segments. Mechanistically, absence of RP2 GAP activity increases ARL3-GTP levels, forcing PDE6D to assume a predominantly "closed" conformation that impedes binding of lipids. Lack of interaction disrupts trafficking of PDE6 and GRK1 to their destination, the photoreceptor outer segments. We propose that hyperactivity of ARL3-GTP in RP2 knockout mice and human patients with RP2 null alleles leads to XLRP resembling recessive rod-cone dystrophy.
The polarization signatures of blazar emissions are known to be highly variable. In addition to small fluctuations of the polarization angle around a mean value, large (greater than or similar to 180 degrees) polarization angle swings are sometimes observed. We suggest that such phenomena can be interpreted as arising from light travel time effects within an underlying axisymmetric emission region. We present the first simultaneous fitting of the multi-wavelength spectrum, variability, and time-dependent polarization features of a correlated optical and gamma-ray flaring event of the prominent blazar 3C279, which was accompanied by a drastic change in its polarization signatures. This unprecedented combination of spectral, variability, and polarization information in a coherent physical model allows us to place stringent constraints on the particle acceleration and magnetic field topology in the relativistic jet of a blazar, strongly favoring a scenario in which magnetic energy dissipation is the primary driver of the flare event.
Swelling of Polyelectrolyte Multilayers: The Relation Between, Surface and Bulk Characteristics
(2015)
The odd even effect, i.e., the influence of the outermost layer of polyelectrolyte multilayers (PEMs) on their swelling behavior, is investigated. For that purpose poly(styrene sodium sulfonate) (PSS)/poly(diallyl-dimethylammonium chloride) (PDADMAC) polyelectrolyte multilayers are studied in air with 1% relative humidity (RH), 30% RH, 95% RH, and in liquid water by ellipsometry, atomic force microscopy (AFM), and X-ray reflectometry (XRR). Since the total amount of water uptake in swollen PEMs is divided into two fractions, the void water and the swelling water, a correct evaluation of the odd even effect is only possible if both fractions are examined separately. In order to allow measuring samples over a larger thickness regime the investigation of a larger amount of samples is required. Therefore, the concept of separating void water from swelling water using neutron reflectometry is for the first time transferred to ellipsometry. The subsequent analysis of swelling water, void water, and roughness revealed the existence of two types of odd even effects: an odd even effect which addresses only the surface of the PEM (surface-odd even effect) and an odd even effect which addresses also the bulk of the PEM (bulk-odd even effect). The appearance of both effects is dependent on the environment; the surface-odd even effect is only detectable in humid air while the bulk-odd even effect is only detectable in liquid water. The bulk-odd even effect is related to the osmotic pressure between the PEM and the surrounding water. A correlation between the amount of void water and both odd even effects is not found. The amount of void water is independent of the terminated layer and the thickness of PEMs.
A direct electron transfer (DET) based sulphite/oxygen biofuel cell is reported that utilises human sulphite oxidase (hSOx) and Myrothecium verrucaria bilirubin oxidase (MvBOx) and nanostructured gold electrodes. For bioanode construction, the nanostructured gold microelectrodes were further modified with 3,3'-dithiodipropionic acid di(N-hydroxysuccinimide ester) to which polyethylene imine was covalently attached. hSOx was adsorbed onto this chemically modified nanostructured electrode with high surface loading of electroactive enzyme and in presence of sulphite high anodic bioelectrocatalytic currents were generated with an onset potential of 0.05 V vs. NHE. The biocathode contained MyBOx directly adsorbed to the deposited gold nanoparticles for cathodic oxygen reduction starting at 0.71 V vs. NHE. Both enzyme electrodes were integrated to a DET-type biofuel cell. Power densities of 8 and 1 mu W cm(-2) were achieved at 0.15 V and 0.45 V of cell voltages, respectively, with the membrane based biodevices under aerobic conditions. (C) 2014 Elsevier B.V. All rights reserved.
The bioelectrocatalytic sulfite oxidation by human sulfite oxidase (hSO) on indium tin oxide (ITO) is reported, which is facilitated by functionalizing of the electrode surface with polyethylenimine (PEI)-entrapped CdS nanoparticles and enzyme. hSO was assembled onto the electrode with a high surface loading of electroactive enzyme. In the presence of sulfite but without additional mediators, a high bioelectrocatalytic current was generated. Reference experiments with only PEI showed direct electron transfer and catalytic activity of hSO, but these were less pronounced. The application of the polyelectrolyte-entrapped quantum dots (QDs) on ITO electrodes provides a compatible surface for enzyme binding with promotion of electron transfer. Variations of the buffer solution conditions, e.g., ionic strength, pH, viscosity, and the effect of oxygen, were studied in order to understand intramolecular and heterogeneous electron transfer from hSO to the electrode. The results are consistent with a model derived for the enzyme by using flash photolysis in solution and spectroelectrochemistry and molecular dynamic simulations of hSO on monolayer-modified gold electrodes. Moreover, for the first time a photoelectrochemical electrode involving immobilized hSO is demonstrated where photoexcitation of the CdS/hSO-modified electrode lead to an enhanced generation of bioelectrocatalytic currents upon sulfite addition. Oxidation starts already at the redox potential of the electron transfer domain of hSO and is greatly increased by application of a small overpotential to the CdS/hSO-modified ITO.
The electrophoretic deposition process was used to produce multi-layered ceramics consisting of alternating layers of fully stabilized cubic zirconia and partially stabilized tetragonal zirconia to make use of their different mechanical behaviour, investigating the possibility to deflect advancing cracks at the interfaces of the different layers. This crack deflection is apparently impacted by a toughening mechanism only found in the tetragonal stabilized zirconia polymorph and is characterized by the stress induced transformation of the metastable tetragonal phase into the monoclinic one, which is accompanied by a volume increase resulting in a closing mechanism for advancing cracks.
While improving the electrophoretic deposition process, we investigated the transformation toughening mechanism at the layer interfaces and their effect on crack propagation. Investigations involved a combination of different imaging methods, including light microscopy, white light interferometry, atomic force microscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy and Raman spectroscopy.
We propose a fibre-based approach for generation of optical frequency combs (OFCs) with the aim of calibration of astronomical spectrographs in the low and medium-resolution range. This approach includes two steps: in the first step, an appropriate state of optical pulses is generated and subsequently moulded in the second step delivering the desired OFC. More precisely, the first step is realised by injection of two continuous-wave (CW) lasers into a conventional single-mode fibre, whereas the second step generates a broad OFC by using the optical solitons generated in step one as initial condition. We investigate the conversion of a bichromatic input wave produced by two initial CW lasers into a train of optical solitons, which happens in the fibre used as step one. Especially, we are interested in the soliton content of the pulses created in this fibre. For that, we study different initial conditions (a single cosine-hump, an Akhmediev breather, and a deeply modulated bichromatic wave) by means of soliton radiation beat analysis and compare the results to draw conclusion about the soliton content of the state generated in the first step. In case of a deeply modulated bichromatic wave, we observed the formation of a collective soliton crystal for low input powers and the appearance of separated solitons for high input powers. An intermediate state showing the features of both, the soliton crystal and the separated solitons, turned out to be most suitable for the generation of OFC for the purpose of calibration of astronomical spectrographs.
We investigate the generation of optical frequency combs through a cascade of four-wave mixing processes in nonlinear fibres with optimised parameters. The initial optical field consists of two continuous-wave lasers with frequency separation larger than 40 GHz (312.7 pm at 1531 nm). It propagates through three nonlinear fibres. The first fibre serves to pulse shape the initial sinusoidal-square pulse, while a strong pulse compression down to sub-100 fs takes place in the second fibre which is an amplifying erbium-doped fibre. The last stage is a low-dispersion highly nonlinear fibre where the frequency comb bandwidth is increased and the line intensity is equalised. We model this system using the generalised nonlinear Schrodinger equation and investigate it in terms of fibre lengths, fibre dispersion, laser frequency separation and input powers with the aim to minimise the frequency comb noise. With the support of the numerical results, a frequency comb is experimentally generated, first in the near infra-red and then it is frequency-doubled into the visible spectral range. Using a MUSE-type spectrograph, we evaluate the comb performance for astronomical wavelength calibration in terms of equidistancy of the comb lines and their stability.
Breaking down complexity
(2015)
The unbounded expressive capacity of human language cannot boil down to an infinite list of sentences stored in a finite brain. Our linguistic knowledge is rather grounded around a rule-based universal syntactic computation—called Merge—which takes categorized units in input (e.g. this and ship), and generates structures by binding words recursively into more complex hierarchies of any length (e.g. this ship; this ship sinks…). Here we present data from different fMRI datasets probing the cortical implementation of this fundamental process. We first pushed complexity down to a three-word level, to explore how Merge creates minimally hierarchical phrases and sentences. We then moved to the most fundamental two-word level, to directly assess the universal invariant nature of Merge, when no additive mechanisms are involved. Our most general finding is that Merge as the basic syntactic operation is primarily performed by confined area, namely BA 44 in the IFG. Activity reduces to its most ventral-anterior portion at the most fundamental level, following fine-grained sub-anatomical parcellation proposed for the region. The deep frontal operculum/anterior-dorsal insula (FOP/adINS), a phylogenetically older and less specialized region, rather appears to support word-accumulation processing in which the categorical information of the word is first accessed based on its lexical status, and then maintained on hold before further processing takes place. The present data confirm the general notion of BA 44 being activated as a function of complex structural hierarchy, but they go beyond this view by proposing that structural sensitivity in BA 44 is already appreciated at the lowest levels of complexity during which minimal phrase-structures are build up, and syntactic Merge is assessed. Further, they call for a redefinition of BA 44 from multimodal area to a macro-region with internal localizable functional profiles
Poly(Ionic Liquid)s
(2015)
The biosynthesis of the molybdenum cofactor (Moco) has been intensively studied, in addition to its insertion into molybdoenzymes. In particular, a link between the assembly of molybdoenzymes and the biosynthesis of FeS clusters has been identified in the recent years: 1) the synthesis of the first intermediate in Moco biosynthesis requires an FeS-cluster containing protein, 2) the sulfurtransferase for the dithiolene group in Moco is also involved in the synthesis of FeS clusters, thiamin and thiolated tRNAs, 3) the addition of a sulfido-ligand to the molybdenum atom in the active site additionally involves a sulfurtransferase, and 4) most molybdoenzymes in bacteria require FeS clusters as redox active cofactors. In this review we will focus on the biosynthesis of the molybdenum cofactor in bacteria, its modification and insertion into molybdoenzymes, with an emphasis to its link to FeS cluster biosynthesis and sulfur transfer. (C) 2014 Elsevier B.V. All rights reserved.
X-ray spectroscopy is a powerful tool to study the local charge distribution of chemical systems. Together with the liquid jet it becomes possible to probe chemical systems in their natural environment, the liquid phase. In this work, we present X-ray absorption (XA), X-ray emission (XE) and resonant inelastic X-ray scattering (RIXS) data of pure water and various salt solutions and show the possibilities these methods offer to elucidate the nature of ion-water interaction.
An electrochemical assay for the indication of the activity of the cell bound differentiation marker alkaline phosphatase (ALP) is proposed using voltammetry on an in-vitro cell culture. The basis of the assay is cultivation of cells on gold microelectrodes in wells of a microplate, catalytic hydrolysis of p-aminophenyl phosphate by ALP and indication of p-aminophenol oxidation by square wave voltammetry (SWV) with the sensors onto which the cells attached. The morphology of the bone marrow stromal cell line (MBA-15) on the electrode surface was investigated and it exhibited in vitro osteogenic characteristics. Since ALP is expressed on the cell surface in early differentiation stage of osteoblastic cells, its activity was followed after different culture times over a period of 144 h by recording repetitive voltammograms at different time points upon addition of the substrate p-aminophenyl phosphate. The ALP activity was estimated from the signal increase related to formation rate of p-aminophenol and the number of cells. The highest value was measured at 120 h, when the cells reached confluence. The results of the electrochemical activity assay are consistent with the colorimetric acquired value from p-nitrophenol formation rate.
Hybrid architectures which combine a MIP with an immobilized affinity ligand or a biocatalyst sum up the advantages of both components. In this paper, hybrid architectures combining a layer of a molecularly imprinted electropolymer with a mini-enzyme or a self-assembled monolayer will be presented. (i) Microperoxidase-11 (MP-11) catalyzed oxidation of the drug aminopyrine on a product-imprinted sublayer: The peroxide dependent conversion of the analyte aminopyrine takes place in the MP-11 containing layer on top of a product-imprinted electropolymer on the indicator electrode. The hierarchical architecture resulted in the elimination of interfering signals for ascorbic acid and uric acid. An advantage of the new hierarchical structure is the separation of MIP formation by electropolymerization and immobilization of the catalyst. In this way it was for the first time possible to integrate an enzyme with a MIP layer in a sensor configuration. This combination has the potential to be transferred to other enzymes, e.g. P450, opening the way to clinically important analytes. (ii) Epitope-imprinted poly-scopoletin layer for binding of the C-terminal peptide and cytochrome c (Cyt c): The MIP binds both the target peptide and the parent protein almost eight times stronger than the non-imprinted polymer with affinities in the lower micromolar range. Exchange of only one amino acid in the peptide decreases the binding by a factor of five. (iii) MUA-poly-scopoletin MIP for cytochrome c: Cyt c bound to the MIP covered gold electrode exhibits direct electron transfer with a redox potential and rate constant typical for the native protein. The MIP cover layer suppresses the displacement of the target protein by BSA or myoglobin. The combination of protein imprinted polymers with an efficient electron transfer is a new concept for characterizing electroactive proteins such as Cyt c. The competition with other proteins shows that the MIP binds its target Cyt c preferentially and that molecular shape and the charge of protein determine the binding of interfering proteins.
The Tian Shan range is an inherited intracontinental structure reactivated by the far-field effects of the India-Asia collision. A growing body of thermochronology and magnetostratigraphy datasets shows that the range grew through several tectonic pulses since similar to 25 Ma, however the early Cenozoic history remains poorly constrained. The time-lag between the Eocene India-Asia collision and the Miocene onset of Tian Shan exhumation is particularly enigmatic. This peculiar period is potentially recorded along the southwestern Tian Shan piedmont. There, late Eocene marine deposits of the proto-Paratethys epicontinental sea transition to continental foreland basin sediments of unknown age were recently dated. We provide magnetostratigraphic dating of these continental sediments from the 1700-m-thick Mine section integrated with previously published detrital apatite fission track and U/Pb zircon ages. The most likely correlation to the geomagnetic polarity time scale indicates an age span from 20.8 to 13.3 Ma with a marked increase in accumulation rates at 19-18 Ma. This implies that the entire Oligocene period is missing between the last marine and first continental sediments, as suggested by previous southwestern Tian Shan results. This differs from the southwestern Tarim basin where Eocene marine deposits are continuously overlain by late Eocene-Oligocene continental sediments. This supports a simple evolution model of the western Tarim basin with Eocene-Oligocene foreland basin activation to the south related to northward thrusting of the Kunlun Shan, followed by early Miocene activation of northern foreland basin related to overthrusting of the south Tian Shan. Our data also support southward propagation of the Tian Shan piedmont from 20 to 18 Ma that may relate to motion on the Talas Fergana Fault. The coeval activation of a major right-lateral strike-slip system allowing indentation of the Pamir Salient into the Tarim basin, suggests far-field deformation from the India-Asia collision zone affected the Tian Shan and the Talas Fergana fault by early Miocene. (C) 2015 Elsevier B.V. All rights reserved.
A multiblock copolymer termed as PCL-PIBMD, consisting of crystallizable poly(epsilon-caprolactone) (PCL) segments and crystallizable poly(3S-isobutyl-morpholine-2,5-dione) (PIBMD) segments, has been reported as a material showing a thermally-induced shape-memory effect. While PIBMD crystalline domains act as netpoints to determine the permanent shape, both PCL crystalline domains and PIBMD amorphous domains, which have similar transition temperatures (T-trans) can act as switching domains. In this work, the influence of the deformation temperature (T-deform = 50 or 20 degrees C), which was above or below T-trans, on the structural changes of PCL-PIBMD during uniaxial deformation and the shapememory properties were investigated. Furthermore, the relative contribution of crystalline PCL and PIBMD amorphous phases to the fixation of the temporary shape were distinguished by a toluene vapor treatment approach. The results indicated that at 50 degrees C, both PCL and PIBMD amorphous phases can be orientated during deformation, resulting in thermally-induced crystals of PCL domains and joint contribution to the switching domains. In contrast at 20 degrees C, the temporary shape was mainly fixed by PCL crystals generated via strain-induced crystallization.
The present study explored the perceptual span (i.e., the physical extent of an area from which useful visual information is extracted during a single fixation) during the reading of Chinese sentences in 2 experiments. In Experiment 1, we tested whether the rightward span can go beyond 3 characters when visually similar masks were used. Results showed that Chinese readers needed at least 4 characters to the right of fixation to maintain a normal reading behavior when visually similar masks were used and when characters were displayed in small fonts, indicating that the span is dynamically influenced by masking materials. In Experiments 2 and 3, we asked whether the perceptual span varies as a function of font size in spaced (German) and unspaced (Chinese) scripts. Results clearly suggest perceptual span depends on font size in Chinese, but we failed to find such evidence for German. We propose that the perceptual span in Chinese is flexible; it is strongly constrained by its language-specific properties such as high information density and lack of word spacing. Implications for saccade-target selection during the reading of Chinese sentences are discussed.
Despite the well-known influence of emotional meaning on cognition, relatively less is known about its effects on reading behavior. We investigated whether fixation behavior during the reading of Chinese sentences is influenced by emotional word meaning in the parafovea. Two-character target words embedded into the same sentence frames provided emotionally positive, negative, or neutral contents. Fixation durations on neutral pretarget words were prolonged for positive parafoveal words and for highly frequent negative parafoveal words. In addition, fixation durations on foveal emotional words were shorter than those on neutral words. We also found that the role of emotional words varied as a function of their valence during foveal and parafoveal processing. These findings suggest a processing advantage for emotional words relative to emotionally neutral stimuli in foveal and parafoveal vision. We discuss implications for the notion of attention attraction due to emotional content.
In the present study, we manipulated different types of information available in the parafovea during the reading of Chinese sentences and examined how deaf readers make use of the parafoveal information. Results clearly indicate that although the reading-level matched hearing readers make greater use of orthographic information in the parafovea, parafoveal semantic information is obtained earlier among the deaf readers. In addition, a phonological preview benefit effect was found for the better deaf readers (relative to less-skilled deaf readers), although we also provide an alternative explanation for this effect. Providing evidence that Chinese deaf readers have higher efficiency when processing parafoveal semantics, the study indicates flexibility across individuals in the mechanisms underlying word recognition adapting to the inputs available in the linguistic environment.
This study investigates the effect of foveal load (i.e., processing difficulty of currently fixated words) on parafoveal information processing. Contrary to the commonly accepted view that high foveal load leads to reduced parafoveal processing efficiency, results of the present study showed that increasing foveal visual (but not linguistic) processing load actually increased the amount of parafoveal information acquired, presumably due to the fact that longer fixation duration on the pretarget word provided more time for parafoveal processing of the target word. It is therefore proposed in the present study that foveal linguistic processing load is not the only factor that determines parafoveal processing; preview time (afforded by foveal word visual processing load) may jointly influence parafoveal processing. (C) 2015 Elsevier Ltd. All rights reserved.
Here, we report on two photosensitive amorphous polymers showing opposite behavior upon exposure to illumination. The first polymer (PAZO) consists of linear backbone to which azobenzene-containing side chains are covalently attached, while in the second polymer (azo-PEI), the azobenzene side chains are attached ionically to a polyelectrolyte backbone. When irradiated through a mask, the PAZO goes away from the intensity maxima, leaving behind topography trenches, while the direction of the mass transport of the azo-PEI polymer points towards the intensity maxima. This kind of behavior has been reported only for certain liquid crystalline polymers that exhibit in-phase reaction on illumination, that is, topography maxima coincides with the intensity maxima. Furthermore, flat nanocrystals placed on top of azo-PEI film was found to be moved together with the mass transport of the underlying polymer film as visualized using in situ atomic force microscopy (AFM) measurements. It was also demonstrated that the two polymer films respond differently on irradiation with the polarization and intensity interference patterns (IPs). To record the kinetic of the surface relief grating formation within two polymers during irradiation with different IPs, we utilized a homemade setup combining the optical part for the generation of IP and AFM. A possible mechanism explaining different responses on the irradiation of amorphous polymers is discussed in the frame of a theoretical model proposed by Saphiannikova et al. (J. Phys. Chem. B 113, 5032-5045 (2009)).
Here, a new method for enhancing the photoelectrochemical properties of carbon nitride thin films by in situ supramolecular-driven preorganization of phenyl-contained monomers in molten sulfur is reported. A detailed analysis of the chemical and photophysical properties suggests that the molten sulfur can texture the growth and induce more effective integration of phenyl groups into the carbon nitride electrodes, resulting in extended light absorption alongside with improved conductivity and better charge transfer. Furthermore, photophysical measurements indicate the formation of sub-bands in the optical bandgap which is beneficial for exciton splitting. Moreover, the new bands can mediate hole transfer to the electrolyte, thus improving the photooxidation activity. The utilization of high temperature solvent as the polymerization medium opens new opportunities for the significant improvement of carbon nitride films toward an efficient photoactive material for various applications.
We show that coadsorbed oxygen atoms have a dramatic influence on the CO desorption dynamics from Ru(0001). In contrast to the precursor-mediated desorption mechanism on Ru(0001), the presence of surface oxygen modifies the electronic structure of Ru atoms such that CO desorption occurs predominantly via the direct pathway. This phenomenon is directly observed in an ultrafast pump-probe experiment using a soft x-ray free-electron laser to monitor the dynamic evolution of the valence electronic structure of the surface species. This is supported with the potential of mean force along the CO desorption path obtained from density-functional theory calculations. Charge density distribution and frozen-orbital analysis suggest that the oxygen-induced reduction of the Pauli repulsion, and consequent increase of the dative interaction between the CO 5 sigma and the charged Ru atom, is the electronic origin of the distinct desorption dynamics. Ab initio molecular dynamics simulations of CO desorption from Ru(0001) and oxygen-coadsorbed Ru(0001) provide further insights into the surface bond-breaking process.
Reply to Peng et al.: Archaeological contexts should not be ignored for early chicken domestication
(2015)
This work elucidates the impact of charge transport on the photovoltaic properties of organic solar cells. Here we show that the analysis of current-voltage curves of organic solar cells under illumination with the Shockley equation results in values for ideality factor, photo-current and parallel resistance, which lack physical meaning. Drift-diffusion simulations for a wide range of charge-carrier mobilities and illumination intensities reveal significant carrier accumulation caused by poor transport properties, which is not included in the Shockley equation. As a consequence, the separation of the quasi Fermi levels in the organic photoactive layer (internal voltage) differs substantially from the external voltage for almost all conditions. We present a new analytical model, which considers carrier transport explicitly. The model shows excellent agreement with full drift-diffusion simulations over a wide range of mobilities and illumination intensities, making it suitable for realistic efficiency predictions for organic solar cells.
In recent years, core/shell nanohybrids containing a nanoparticle core and a distinct surrounding shell of polymer brushes have received extensive attention in nanoelectronics, nanophotonics, catalysis, nanopatterning, drug delivery, biosensing, and many others. From the large variety of existing polymerization methods on the one hand and strategies for grafting onto nanoparticle surfaces on the other hand, the combination of grafting-from with controlled radical polymerization (CRP) techniques has turned out to be the best suited for synthesizing these well-defined core/shell nanohybrids and is known as surface-initiated CRP. Most common among these are surface-initiated atom transfer radical polymerization (ATRP), surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization, and surface-initiated nitroxide-mediated polymerization (NMP). This review highlights the state of the art of growing polymers from nanoparticles using surface-initiated CRP techniques. We focus on mechanistic aspects, synthetic procedures, and the formation of complex architectures as well as novel properties. From the vast number of examples of nanoparticle/polymer hybrids formed by surface-initiated CRP techniques, we present nanohybrid formation from the particularly important and most studied silica nanoparticles, gold nanocrystals, and proteins which can be regarded as bionanoparticles.
The Implicit Association Test (IAT) aims to measure participants' automatic evaluation of an attitude object and is useful especially for the measurement of attitudes related to socially sensitive subjects, e.g. doping in sports. Several studies indicate that IAT scores can be faked on instruction. But fully or semi-instructed research scenarios might not properly reflect what happens in more realistic situations, when participants secretly decide to try faking the test. The present study is the first to investigate IAT faking when there is only an implicit incentive to do so. Sixty-five athletes (22.83 years +/- 2.45; 25 women) were randomly assigned to an incentive-to-fake condition or a control condition. Participants in the incentive-to-fake condition were manipulated to believe that athletes with lenient doping attitudes would be referred to a tedious 45-minute anti-doping program. Attitudes were measured with the pictorial doping brief IAT (BIAT) and with the Performance Enhancement Attitude Scale (PEAS). A one-way MANOVA revealed significant differences between conditions after the manipulation in PEAS scores, but not in the doping BIAT. In the light of our hypothesis this suggests that participants successfully faked an exceedingly negative attitude to doping when completing the PEAS, but were unsuccessful in doing so on the reaction time-based test. This study assessed BIAT faking in a setting that aimed to resemble a situation in which participants want to hide their attempts to cheat. The two measures of attitude were differentially affected by the implicit incentive. Our findings provide evidence that the pictorial doping BIAT is relatively robust against spontaneous and naive faking attempts. (B) IATs might be less prone to faking than implied by previous studies.
Continuing advances in 'omics methodologies and instrumentation is enhancing the understanding of how plants cope with the dynamic nature of their growing environment. 'Omics platforms have been only recently extended to cover horticultural crop species. Many of the most widely cultivated vegetable crops belong to the genus Brassica: these include plants grown for their root (turnip, rutabaga/swede), their swollen stem base (kohlrabi), their leaves (cabbage, kale, pak choi) and their inflorescence (cauliflower, broccoli). Characterization at the genome, transcript, protein and metabolite levels has illustrated the complexity of the cellular response to a whole series of environmental stresses, including nutrient deficiency, pathogen attack, heavy metal toxicity, cold acclimation, and excessive and sub optimal irradiation. This review covers recent applications of omics technologies to the brassicaceous vegetables, and discusses future scenarios in achieving improvements in crop end-use quality.
Diarylethene derivatives are photochromic molecular switches, undergoing a ring-opening/-closing reaction by illumination with light. The symmetry of the closed form is determined by the WoodWard Hoffinann rules according to which the reaction proceeds by corirotatory rotation -in that case. Here, we show by a cOrnbined approach of scanning tunneling microscopy (STM) and density functional theory (DFT) calculations that the Open isomer of 4,4'-(4,4'-(perfluorocydopent-1-ene-1,2-diyl)bis(5-methyl-thiophent-4,2,4-dipyridine) (PDTE) retains its open form upon adsorption on a Ag(111) surface. It caribe switched into a closed form, which we identify as the digrotatOly cydization product, by controlled manipulation 'With the STM tip, Evidence of an electric-field dependent switching-process 'is interpreted on the basis of a Simple electroStatic Model, which suggests that the reaction proceedS via an "upright" intermediate state. This pathway thus strongly differs from the switching reaction in solution.