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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.
Analysis and modeling of transient earthquake patterns and their dependence on local stress regimes
(2015)
Investigations in the field of earthquake triggering and associated interactions, which includes aftershock triggering as well as induced seismicity, is important for seismic hazard assessment due to earthquakes destructive power. One of the approaches to study earthquake triggering and their interactions is the use of statistical earthquake models, which are based on knowledge of the basic seismicity properties, in particular, the magnitude distribution and spatiotemporal properties of the triggered events.
In my PhD thesis I focus on some specific aspects of aftershock properties, namely, the relative seismic moment release of the aftershocks with respect to the mainshocks; the spatial correlation between aftershock occurrence and fault deformation; and on the influence of aseismic transients on the aftershock parameter estimation. For the analysis of aftershock sequences I choose a statistical approach, in particular, the well known Epidemic Type Aftershock Sequence (ETAS) model, which accounts for the input of background and triggered seismicity. For my specific purposes, I develop two ETAS model modifications in collaboration with Sebastian Hainzl. By means of this approach, I estimate the statistical aftershock parameters and performed simulations of aftershock sequences as well.
In the case of seismic moment release of aftershocks, I focus on the ratio of cumulative seismic moment release with respect to the mainshocks. Specifically, I investigate the ratio with respect to the focal mechanism of the mainshock and estimate an effective magnitude, which represents the cumulative aftershock energy (similar to Bath's law, which defines the average difference between mainshock and the largest aftershock magnitudes). Furthermore, I compare the observed seismic moment ratios with the results of the ETAS simulations. In particular, I test a restricted ETAS (RETAS) model which is based on results of a clock advanced model and static stress triggering.
To analyze spatial variations of triggering parameters I focus in my second approach on the aftershock occurrence triggered by large mainshocks and the study of the aftershock parameter distribution and their spatial correlation with the coseismic/postseismic slip and interseismic locking. To invert the aftershock parameters I improve the modified ETAS (m-ETAS) model, which is able to take the extension of the mainshock rupture into account. I compare the results obtained by the classical approach with the output of the m-ETAS model.
My third approach is concerned with the temporal clustering of seismicity, which might not only be related to earthquake-earthquake interactions, but also to a time-dependent background rate, potentially biasing the parameter estimations. Thus, my coauthors and I also applied a modification of the ETAS model, which is able to take into account time-dependent background activity. It can be applicable for two different cases: when an aftershock catalog has a temporal incompleteness or when the background seismicity rate changes with time, due to presence of aseismic forces.
An essential part of any research is the testing of the developed models using observational data sets, which are appropriate for the particular study case. Therefore, in the case of seismic moment release I use the global seismicity catalog. For the spatial distribution of triggering parameters I exploit two aftershock sequences of the Mw8.8 2010 Maule (Chile) and Mw 9.0 2011 Tohoku (Japan) mainshocks. In addition, I use published geodetic slip models of different authors. To test our ability to detect aseismic transients my coauthors and I use the data sets from Western Bohemia (Central Europe) and California.
Our results indicate that:
(1) the seismic moment of aftershocks with respect to mainshocks depends on the static stress changes and is maximal for the normal, intermediate for thrust and minimal for strike-slip stress regimes, where the RETAS model shows a good correspondence with the results;
(2) The spatial distribution of aftershock parameters, obtained by the m-ETAS model, shows anomalous values in areas of reactivated crustal fault systems. In addition, the aftershock density is found to be correlated with coseismic slip gradient, afterslip, interseismic coupling and b-values. Aftershock seismic moment is positively correlated with the areas of maximum coseismic slip and interseismically locked areas. These correlations might be related to the stress level or to material properties variations in space;
(3) Ignoring aseismic transient forcing or temporal catalog incompleteness can lead to the significant under- or overestimation of the underlying trigger parameters. In the case when a catalog is complete, this method helps to identify aseismic sources.
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.
Optical frequency combs (OFC) constitute an array of phase-correlated equidistant spectral lines with nearly equal intensities over a broad spectral range. The adaptations of combs generated in mode-locked lasers proved to be highly efficient for the calibration of high-resolution (resolving power > 50000) astronomical spectrographs. The observation of different galaxy structures or the studies of the Milky Way are done using instruments in the low- and medium resolution range. To such instruments belong, for instance, the Multi Unit Spectroscopic Explorer (MUSE) being developed for the Very Large Telescope (VLT) of the European Southern Observatory (ESO) and the 4-metre Multi-Object Spectroscopic Telescope (4MOST) being in development for the ESO VISTA 4.1 m Telescope. The existing adaptations of OFC from mode-locked lasers are not resolvable by these instruments.
Within this work, a fibre-based approach for generation of OFC specifically in the low- and medium resolution range is studied numerically. This approach consists of three optical fibres that are fed by two equally intense continuous-wave (CW) lasers. The first fibre is a conventional single-mode fibre, the second one is a suitably pumped amplifying Erbium-doped fibre with anomalous dispersion, and the third one is a low-dispersion highly nonlinear optical fibre. The evolution of a frequency comb in this system is governed by the following processes: as the two initial CW-laser waves with different frequencies propagate through the first fibre, they generate an initial comb via a cascade of four-wave mixing processes. The frequency components of the comb are phase-correlated with the original laser lines and have a frequency spacing that is equal to the initial laser frequency separation (LFS), i.e. the difference in the laser frequencies. In the time domain, a train of pre-compressed pulses with widths of a few pico-seconds arises out of the initial bichromatic deeply-modulated cosine-wave. These pulses undergo strong compression in the subsequent amplifying Erbium-doped fibre: sub-100 fs pulses with broad OFC spectra are formed. In the following low-dispersion highly nonlinear fibre, the OFC experience a further broadening and the intensity of the comb lines are fairly equalised. This approach was mathematically modelled by means of a Generalised Nonlinear Schrödinger Equation (GNLS) that contains terms describing the nonlinear optical Kerr effect, the delayed Raman response, the pulse self-steepening, and the linear optical losses as well as the wavelength-dependent Erbium gain profile for the second fibre. The initial condition equation being a deeply-modulated cosine-wave mimics the radiation of the two initial CW lasers. The numerical studies are performed with the help of Matlab scripts that were specifically developed for the integration of the GNLS and the initial condition according to the proposed approach for the OFC generation. The scripts are based on the Fourth-Order Runge-Kutta in the Interaction Picture Method (RK4IP) in combination with the local error method.
This work includes the studies and results on the length optimisation of the first and the second fibre depending on different values of the group-velocity dispersion of the first fibre. Such length optimisation studies are necessary because the OFC have the biggest possible broadband and exhibit a low level of noise exactly at the optimum lengths. Further, the optical pulse build-up in the first and the second fibre was studied by means of the numerical technique called Soliton Radiation Beat Analysis (SRBA). It was shown that a common soliton crystal state is formed in the first fibre for low laser input powers. The soliton crystal continuously dissolves into separated optical solitons as the input power increases. The pulse formation in the second fibre is critically dependent on the features of the pulses formed in the first fibre. I showed that, for low input powers, an adiabatic soliton compression delivering low-noise OFC occurs in the second fibre. At high input powers, the pulses in the first fibre have more complicated structures which leads to the pulse break-up in the second fibre with a subsequent degradation of the OFC noise performance. The pulse intensity noise studies that were performed within the framework of this thesis allow making statements about the noise performance of an OFC. They showed that the intensity noise of the whole system decreases with the increasing value of LFS.
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.
An increasing demand on functionality and flexibility leads to an integration of beforehand isolated system solutions building a so-called System of Systems (SoS). Furthermore, the overall SoS should be adaptive to react on changing requirements and environmental conditions. Due SoS are composed of different independent systems that may join or leave the overall SoS at arbitrary point in times, the SoS structure varies during the systems lifetime and the overall SoS behavior emerges from the capabilities of the contained subsystems. In such complex system ensembles new demands of understanding the interaction among subsystems, the coupling of shared system knowledge and the influence of local adaptation strategies to the overall resulting system behavior arise. In this report, we formulate research questions with the focus of modeling interactions between system parts inside a SoS. Furthermore, we define our notion of important system types and terms by retrieving the current state of the art from literature. Having a common understanding of SoS, we discuss a set of typical SoS characteristics and derive general requirements for a collaboration modeling language. Additionally, we retrieve a broad spectrum of real scenarios and frameworks from literature and discuss how these scenarios cope with different characteristics of SoS. Finally, we discuss the state of the art for existing modeling languages that cope with collaborations for different system types such as SoS.
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.
The effect of implicitly incentivized faking on explicit and implicit measures of doping attitude
(2015)
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.
Die vorliegende Arbeit thematisiert die Finanzierungsmodelle von Public-Private-Partnership-Projekten (PPP) und deren Refinanzierung durch die Kapitalgeber.
Dabei wurden zwei zentrale Fragestellungen thematisiert. Erstens: Führen PPPProjekte zu einer Verschuldung der öffentlichen Hand und sind sie entsprechend bei den Berechnungen der Konvergenzkriterien bzw. der Schulden- und Neuverschuldungsquoten zu berücksichtigen? Die zu prüfende Arbeitshypothese geht von einer Verschuldung der öffentlichen Hand in Folge von PPP-Projekten aus. Zweitens: Unterstellt wird eine bedeutsame Funktion von PPP für die Infrastrukturfinanzierung, wobei im Sinne einer Effizienzsteigerung die Passgenauigkeit beziehungsweise Konsistenz der haushaltsrechtlichen Regelungen mit den regulatorischen Vorgaben für die Kapitalgeber von PPP-Projekten analysiert wird. Diese Schnittstelle und die zur Generierung günstiger („kommunalähnlicher") Finanzierungskonditionen notwendigen staatlichen Garantien bei PPP drängt geradezu zu einem ordnungspolitischen Vergleich von Ansätzen bzw. Projekten im Bereich PPP und in Cash-Flow-Kalkülen.
Die Arbeit führt mit einem gewissen gesamtwirtschaftlichen Fokus der PPP tief in die Analyse des Kapitalmarktes und der Bankenregulierung. Es erfolgt ein Vergleich der gedeckten Refinanzierungsinstrumente für PPP, die durch Forderungen besichert sind (Asset Backed Securities) und solche, die beispielsweise durch Forderungen gegen die öffentliche Hand besichert sind (Covered Bonds). Letztere können auch grundpfandrechtlich gesichert sein. Hier setzt der Verfasser später seine Skizze eines „Infrastructure Covered Bonds" für die Finanzierung notwendiger Infrastrukturmaßnahmen nicht nur in Deutschland an, wobei das Wertpapier hier ausschließlich zur Finanzierung der Infrastruktur bei einem entsprechend neu zuschaffenden (Deckungs-) Registers begeben werden wird.
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.
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.
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.
A large number of experimental findings from neuroscience and experimental psychology demonstrated interactions between spatial cognition and numerical cognition. In particular, many researchers posited a horizontal mental number line, where small numbers are thought of as being to the left of larger numbers. This review synthesizes work on the mental association between space and number, indicating the existence of multiple spatial mappings: recent research has found associations between number and vertical space, as well as associations between number and near/far space. We discuss number space in three dimensions with an eye on potential origins of the different number mappings, and how these number mappings fit in with our current knowledge of brain organization and brain-culture interactions. We derive novel predictions and show how this research fits into a general view of cognition as embodied, grounded and situated. (C) 2015 Elsevier Ltd. All rights reserved.
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.
Bioturbation contributes to soil formation and ecosystem functioning. With respect to the active transport of matter by voles, bioturbation may be considered as a very dynamic process among those shaping soil formation and biogeochemistry. The present study aimed at characterizing and quantifying the effects of bioturbation by voles on soil water relations and carbon and nitrogen stocks. Bioturbation effects were examined based on a field set up in a luvic arenosol comprising of eight 50 x 50 m enclosures with greatly different numbers of common vole (Microtus arvalis L., ca. 35-150 individuals ha(-1) mth(-1)). Eleven key soil variables were analyzed: bulk density, infiltration rate, saturated hydraulic conductivity, water holding capacity, contents of soil organic carbon (SOC) and total nitrogen (N), CO2 emission potential, C/N ratio, the stable isotopic signatures of C-13 and N-15, and pH. The highest vole densities were hypothesized to cause significant changes in some variables within 21 months. Results showed that land history had still a major influence, as eight key variables displayed an additional or sole influence of topography. However, the delta N-15 at depths of 10-20 and 20-30 cm decreased and increased with increasing vole numbers, respectively. Also the CO2 emission potential from soil collected at a depth of 15-30 cm decreased and the C/N ratio at 5-10 cm depth narrowed with increasing vole numbers. These variables indicated the first influence of voles on the respective mineralization processes in some soil layers. Tendencies of vole activity homogenizing SOC and N contents across layers were not significant. The results of the other seven key variables did not confirm significant effects of voles. Thus overall, we found mainly a first response of variables that are indicative for changes in biogeochemical dynamics but not yet of those representing changes in pools.