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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.
Zühlke, Martin ; Riebe, Daniel ; Beitz, Toralf ; Löhmannsröben, Hans-Gerd ; Zenichowski, Karl ; Diener, Marc ; Linscheid, Michael W.
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.
Zurell, Damaris ; Eggers, Ute ; Kaatz, Michael ; Rotics, Shay ; Sapir, Nir ; Wikelski, Martin ; Nathan, Ran ; Jeltsch, Florian
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
Zirafi, Onofrio ; Kim, Kyeong-Ae ; Ständker, Ludger ; Mohr, Katharina B. ; Sauter, Daniel ; Heigele, Anke ; Kluge, Silvia F. ; Wiercinska, Eliza ; Chudziak, Doreen ; Richter, Rudolf ; Möpps, Barbara ; Gierschik, Peter ; Vas, Virag ; Geiger, Hartmut ; Lamla, Markus ; Weil, Tanja ; Burster, Timo ; Zgraja, Andreas ; Daubeuf, Francois ; Frossard, Nelly ; Hachet-Haas, Muriel ; Heunisch, Fabian ; Reichetzeder, Christoph ; Galzi, Jean-Luc ; Perez-Castells, Javier ; Canales-Mayordomo, Angeles ; Jimenez-Barbero, Jesus ; Gimenez-Gallego, Guillermo ; Schneider, Marion ; Shorter, James ; Telenti, Amalio ; Hocher, Berthold ; Forssmann, Wolf-Georg ; Bonig, Halvard ; Kirchhoff, Frank ; Münch, Jan
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.
Current curricular trends require teachers in Baden-
Wuerttemberg (Germany) to integrate Computer Science (CS) into
traditional subjects, such as Physical Science. However, concrete guidelines
are missing. To fill this gap, we outline an approach where a
microcontroller is used to perform and evaluate measurements in the
Physical Science classroom.
Using the open-source Arduino platform, we expect students to acquire
and develop both CS and Physical Science competencies by using a
self-programmed microcontroller. In addition to this combined development
of competencies in Physical Science and CS, the subject matter
will be embedded in suitable contexts and learning environments,
such as weather and climate.
Ziegler, Moritz O. ; Reiter, Karsten ; Heidbach, Oliver ; Zang, Arno ; Kwiatek, Grzegorz ; Stromeyer, Dietrich ; Dahm, Torsten ; Dresen, Georg ; Hofmann, Gerhard
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.
Zhou, Ying ; Zhang, Ling ; Gui, Jiadong ; Dong, Fang ; Cheng, Sihua ; Mei, Xin ; Zhang, Linyun ; Li, Yongqing ; Su, Xinguo ; Baldermann, Susanne ; Watanabe, Naoharu ; Yang, Ziyin
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.
Zhou, Xiqiang ; Chen, Daizhao ; Dong, Shaofeng ; Zhang, Yanqiu ; Guo, Zenghui ; Wei, Hengye ; Yu, Hao
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.
Zhong, Qi ; Metwalli, Ezzeldin ; Rawolle, Monika ; Kaune, Gunar ; Bivigou Koumba, Achille Mayelle ; Laschewsky, André ; Papadakis, Christine M. ; Cubitt, Robert ; Müller-Buschbaum, Peter
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.
Zhang, Houbin ; Hanke-Gogokhia, Christin ; Jiang, Li ; Li, Xiaobo ; Wang, Pu ; Gerstner, Cecilia D. ; Frederick, Jeanne M. ; Yang, Zhenglin ; Baehr, Wolfgang
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.
Zhang, Chaoli ; Li, Chengyuan ; de Grijs, Richard ; Bekki, Kenji ; Deng, Licai ; Zaggia, Simone ; Rubele, Stefano ; Piatti, Andres E. ; Cioni, Maria-Rosa L. ; Emerson, Jim ; For, Bi-Qing ; Ripepi, Vincenzo ; Marconi, Marcella ; Ivanov, Valentin D. ; Chen, Li
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.
Zeng, Ting ; Pankratov, Dmitry ; Falk, Magnus ; Leimkühler, Silke ; Shleev, Sergey ; Wollenberger, Ursula
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.
Zajnulina, Marina ; Böhm, Michael ; Blow, K. ; Rieznik, A. A. ; Giannone, Domenico ; Haynes, Roger ; Roth, Martin M.
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.
Zajnulina, Marina ; Boggio, Jose M. Chavez ; Böhm, Michael ; Rieznik, A. A. ; Fremberg, Tino ; Haynes, Roger ; Roth, Martin M.
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.
Yin, Zhong ; Rajkovic, Ivan ; Veedu, Sreevidya Thekku ; Deinert, Sascha ; Raiser, Dirk ; Jain, Rohit ; Fukuzawa, Hironobu ; Wada, Shin-ichi ; Quevedo, Wilson ; Kennedy, Brian ; Schreck, Simon ; Pietzsch, Annette ; Wernet, Philippe ; Ueda, Kyoshi ; Föhlisch, Alexander ; Techert, Simone
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.
Yang, Wei ; Dupont-Nivet, Guillaume ; Jolivet, Marc ; Guo, Zhaojie ; Bougeois, Laurie ; Bosboom, Roderic ; Zhang, Ziya ; Zhu, Bei ; Heilbronn, Gloria
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)).
Xu, Jingsan ; Shalom, Menny ; Piersimoni, Fortunato ; Antonietti, Markus ; Neher, Dieter ; Brenner, Thomas J. K.
Xu, Jingsan ; Cao, Shaowen ; Brenner, Thomas J. K. ; Yang, Xiaofei ; Yu, Jiaguo ; Antonietti, Markus ; Shalom, Menny
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.
Xin, Hong ; LaRue, Jerry ; Oberg, Henrik ; Beye, Martin ; Turner, J. J. ; Gladh, Jörgen ; Ng, May L. ; Sellberg, Jonas A. ; Kaya, Sarp ; Mercurio, G. ; Hieke, F. ; Nordlund, Dennis ; Schlotter, William F. ; Dakovski, Georgi L. ; Minitti, Michael P. ; Föhlisch, Alexander ; Wolf, Martin ; Wurth, Wilfried ; Ogasawara, Hirohito ; Norskov, Jens K. ; Ostrom, Henrik ; Pettersson, Lars G. M. ; Nilsson, Anders ; Abild-Pedersen, Frank
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.
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.
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.
We compute spectral libraries for populations of coeval stars using state-of-the-art massive-star evolutionary tracks that account for different astrophysics including rotation and close-binarity. Our synthetic spectra account for stellar and nebular contributions. We use our models to obtain E(B – V ), age, and mass for six clusters in spiral galaxy NGC 1566, which have ages of < 50 Myr and masses of > 5 x 104M⊙ according to standard models. NGC 1566 was observed from the NUV to the I-band as part of the imaging Treasury HST program LEGUS: Legacy Extragalactic UV Survey. We aim to establish i) if the models provide reasonable fits to the data, ii) how well the models and photometry are able to constrain the cluster properties, and iii) how different the properties obtained with different models are.
Wirth, Jonas ; Hatter, Nino ; Drost, Robert ; Umbach, Tobias R. ; Barja, Sara ; Zastrow, Matthias ; Rück-Braun, Karola ; Pascual, Jose Ignacio ; Saalfrank, Peter ; Franke, Katharina J.
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.
Wippert, Pia-Maria ; De Witt Huberts, Jessie ; Klipker, Kathrin ; Gantz, Simone ; Schiltenwolf, Marcus ; Mayer, Frank
Back pain is a complex phenomenon that goes beyond a simple medical diagnosis. The aetiology and chronification of back pain can be best described as an interaction between biological, psychological, and social processes. However, to date, multimodal prevention and intervention programs for back pain that target all three aetiological factors have demonstrated limited effectiveness. This lack of supportive evidence for multimodal programmes in the treatment of back pain could be due to the fact that few programs are suitable for long-term and unsupervised use in everyday life. Moreover, in combining the elements from various therapies, little attention has been paid to the mechanisms underlying the synergistic effects of the separate components. In this contribution, we will describe the development of a new multimodal intervention for back pain that set out to address these limitations. To this end, the biological elements of neuromuscular adaptation is supplemented with cognitive behavioral and psychophysiological techniques in an intervention that can be followed at home as well as in clinics, and that is suitable for all grades of pain. The efficacy of this intervention will be tested in a multicentric randomized controlled longitudinal trial (n = 714) at five time points over a period of 6 months. Here we will describe the development and the content of this new intervention.
Small- and large-scale characterization and mixing properties in a thermally driven thin liquid film
(2015)
We study aqueous, freestanding, thin films stabilized by a surfactant with respect to mixing and dynamical systems properties. With this special setup, a two-dimensional fluid can be realized experimentally. The physics of the system involves a complex interplay of thermal convection and interface and gravitational forces. Methodologically, we characterize the system using two classical dynamical systems properties: Lyapunov exponents and entropies. Our experimental setup produces convection with two stable eddies by applying a temperature gradient in one spot that yields weakly turbulent mixing. From dynamical systems theory, one expects a relation of entropies, Lyapunov exponents, a prediction with little experimental support. We can confirm the corresponding statements experimentally, on different scales using different methods. On the small scale the motion and deformation of fluid filaments of equal size (color imaging velocimetry) are used to compute Lyapunov exponents. On the large scale, entropy is computed by tracking the left-right motion of the center fluid jet at the separatrix between the two convection rolls. We thus combine here dynamical systems methods with a concrete application of mixing in a nanoscale freestanding thin film.
Willner, Arne P. ; Barr, Sandra M. ; Glodny, Johannes ; Massonne, Hans-Joachim ; Sudo, Masafumi ; Thomson, Stuart N. ; Van Staal, Cees R. ; White, Chris E.
Ar-40/Ar-39 in situ UV laser ablation of white mica, Rb-Sr mineral isochrons and zircon fission track dating were applied to determine ages of very low- to low-grade metamorphic processes at 3.5 +/- 0.4 kbar, 280 +/- 30 degrees C in the Avalonian Mira terrane of SE Cape Breton Island (Nova Scotia). The Mira terrane comprises Neoproterozoic volcanic-arc rocks overlain by Cambrian sedimentary rocks. Crystallization of metamorphic white mica was dated in six metavolcanic samples by Ar-40/Ar-39 spot age peaks between 396 +/- 3 and 363 +/- 14 Ma. Rb-Sr systematics of minerals and mineral aggregates yielded two isochrons at 389 +/- 7 Ma and 365 +/- 8 Ma, corroborating equilibrium conditions during very low- to low-grade metamorphism. The dated white mica is oriented parallel to foliations produced by sinistral strike-slip faulting and/or folding related to the Middle-Late Devonian transpressive assembly of Avalonian terranes during convergence and emplacement of the neighbouring Meguma terrane. Exhumation occurred earlier in the NW Mira terrane than in the SE. Transpression was related to the closure of the Rheic Ocean between Gondwana and Laurussia by NW-directed convergence. The Ar-40/Ar-39 spot age spectra also display relict age peaks at 477-465 Ma, 439 Ma and 420-428 Ma attributed to deformation and fluid access, possibly related to the collision of Avalonia with composite Laurentia or to earlier Ordovician-Silurian rifting. Fission track ages of zircon from Mira terrane samples range between 242 +/- 18 and 225 +/- 21 Ma and reflect late Palaeozoic reburial and reheating close to previous peak metamorphic temperatures under fluid-absent conditions during rifting prior to opening of the Central Atlantic Ocean.
Observations of the WC9+OB system WR65 in the infrared show variations of its dust emission consistent with a period near 4.8 yr, suggesting formation in a colliding-wind binary (CWB) having an elliptical orbit. If we adopt the IR maximum as zero phase, the times of X-ray maximum count and minimum extinction to the hard component measured by Oskinova & Hamann fall at phases 0.4–0.5, when the separation of the WC9 and OB stars is greatest. We consider WR65 in the context of other WC8–9+OB stars showing dust emission.
Wilke, Franziska Daniela Helena ; Vieth-Hillebrand, Andrea ; Naumann, Rudolf ; Erzinger, Jörg ; Horsfield, Brian
The study reported here evaluates the degree to which metals, salt anions and organic compounds are released from shales by exposure to water, either in its pure form or mixed with additives commonly employed during shale gas exploitation. The experimental conditions used here were not intended to simulate the exploitation process itself, but nevertheless provided important insights into the effects additives have on solute partition behaviour under oxic to sub-oxic redox conditions.
In order to investigate the mobility of major (e.g. Ca, Fe) and trace (e.g. As, Cd, Co, Mo, Pb, U) elements and selected organic compounds, we performed leaching tests with black shale samples from Bornholm, Denmark and Lower Saxony, Germany. Short-term experiments (24 h) were carried out at ambient pressure and temperatures of 100 degrees C using five different lab-made stimulation fluids. Two long-term experiments under elevated pressure and temperature conditions at 100 degrees C/100 bar were performed lasting 6 and 2 months, respectively, using a stimulation fluid containing commercially-available biocide, surfactant, friction reducer and clay stabilizer.
Our results show that the amount of dissolved constituents at the end of the experiment is independent of the pH of the stimulation fluid but highly dependent on the composition of the black shale and the buffering capacity of specific components, namely pyrite and carbonates. Shales containing carbonates buffer the solution at pH 7-8. Sulphide minerals (e.g. pyrite) become oxidized and generate sulphuric acid leading to a pH of 2-3. This low pH is responsible for the overall much larger amount of cations dissolved from shales containing pyrite but little to no carbonate. The amount of elements released into the fluid is also dependent on the residence time, since as much as half of the measured 23 elements show highest concentrations within four days. Afterwards, the concentration of most of the elemental species decreased pointing to secondary precipitations. Generally, in our experiments less than 15% of each analysed element contained in the black shale was mobilised into the fluid. (C) 2015 Elsevier Ltd. All rights reserved.
Ultrahigh-pressure (UHP), coesite-bearing edogites in the Himalaya have been documented from the Kaghan Valley in Pakistan and the Tso Morani area in northwest India. These complexes are part of the northern edge of the Indian plate that has been subducted to, and metamorphosed at, mantle depths of more than 100 km before being exhumed. Both UHP complexes are located today directly adjacent to the Indus-Tsangpo suture zone and are not separated by non-metamorphosed sequences of Tethyan sediments from the Asian margin. Herein, we present new data for one fresh coesite-bearing eclogite from the Tso Moran massif. Therein, garnets are zoned reflecting their growth during prograde and peak metamorphism and showing a thin retrograde overgrowth. Inclusions can be directly correlated to the compositional zoning and are seen as either relicts of the protolith mineral paragenesis and as "snap shots" of the mineral paragenesis during subduction and under peak conditions. Rare earth element concentrations (REE) were obtained for garnet, mineral inclusions in garnet and matrix minerals. The REE pattern in garnet reflects a sequential change in matrix minerals and their proportions due to net transfer reactions during subduction and peak metamorphism. Using conventional geothermobarometry, a peak pressure of ca. 44-48 kbar at 560-760 degrees C followed by an S-shaped exhumation curve has been deduced. Gibbs free energy minimization modelling was used to supplement our analytical findings. (C) 2015 Elsevier B.V. All rights reserved.
Land-use concepts provide decision support for the most efficient usage options according to sustainable development and multifunctionality requirements. However, developments in landscape-related, agricultural production schemes are primarily driven by economic benefits. Therefore, most agricultural land-use concepts tackle particular problems or interests and lack a systemic perspective. As a result, we discuss a conceptual model for future site-specific agricultural land-use with an inbuilt requirement for adequate experimental sites to enable monitoring systems for a new generation of ecosystem models and for new approaches to address science-stakeholder interactions.
Carbon storage capacity of semi-arid grassland soils and sequestration potentials in northern China
(2015)
Wiesmeier, Martin ; Munro, Sam ; Barthold, Frauke Katrin ; Steffens, Markus ; Schad, Peter ; Kögel-Knabner, Ingrid
Organic carbon (OC) sequestration in degraded semi-arid environments by improved soil management is assumed to contribute substantially to climate change mitigation. However, information about the soil organic carbon (SOC) sequestration potential in steppe soils and their current saturation status remains unknown. In this study, we estimated the OC storage capacity of semi-arid grassland soils on the basis of remote, natural steppe fragments in northern China. Based on the maximum OC saturation of silt and clay particles <20m, OC sequestration potentials of degraded steppe soils (grazing land, arable land, eroded areas) were estimated. The analysis of natural grassland soils revealed a strong linear regression between the proportion of the fine fraction and its OC content, confirming the importance of silt and clay particles for OC stabilization in steppe soils. This relationship was similar to derived regressions in temperate and tropical soils but on a lower level, probably due to a lower C input and different clay mineralogy. In relation to the estimated OC storage capacity, degraded steppe soils showed a high OC saturation of 78-85% despite massive SOC losses due to unsustainable land use. As a result, the potential of degraded grassland soils to sequester additional OC was generally low. This can be related to a relatively high contribution of labile SOC, which is preferentially lost in the course of soil degradation. Moreover, wind erosion leads to substantial loss of silt and clay particles and consequently results in a direct loss of the ability to stabilize additional OC. Our findings indicate that the SOC loss in semi-arid environments induced by intensive land use is largely irreversible. Observed SOC increases after improved land management mainly result in an accumulation of labile SOC prone to land use/climate changes and therefore cannot be regarded as contribution to long-term OC sequestration.
Wiese, Stefanie ; Esatbeyoglu, Tuba ; Winterhalter, Peter ; Kruse, Hans-Peter ; Winkler, Stephanie ; Bub, Achim ; Kulling, Sabine E.
Scope: Flavan-3-ols are abundant polyphenols in human nutrition and are associated with beneficial health effects. The aim of this study was to comparatively investigate the metabolic fate of (-)-epicatechin, procyanidin B1, and polymeric procyanidins in a randomized cross-over study in humans.
Methods and results: Parent compounds, conjugates, and microbial metabolites were determined in plasma, urine, and faeces by HPLC-MS and GC-MS/MS. Glucuronidated, sulfated, and methylated (-)-epicatechin and 5-(3',4'-dihydroxyphenyl)-valerolactone were the dominant metabolites in blood and urine. In addition, minor amounts of procyanidin B1 and 4-hydroxy-5-(3',4'-dihydroxyphenyl) valeric acid and their conjugated metabolites were detected. The formation of 5-(3',4'-dihydroxyphenyl)-valerolactone and 4-hydroxy-5-(3',4'-dihydroxyphenyl) valeric acid varied largely between individuals as well as with the degree of polymerization of flavan-3-ols. Monomer units were not detectable in plasma or urine after procyanidin B1 and polymeric procyanidin intake. No correlation was found between the intake of flavan-3-ols and the occurrence of phenolic acids in blood and urine or the phenolic compound profiles in faeces.
Conclusion: In addition to conjugated metabolites derived from the absorption of monomeric flavan-3-ols, 5-(3',4' -dihydroxyphenyl)-valerolactone represents an important in vivo metabolite of (-)-epicatechin and procyanidin B1 produced by the gut microbiota.