A long-standing goal in biomedical imaging, the control of light inside turbid media, requires knowledge of how the phase and amplitude of an illuminating wavefront are transformed as the electric field propagates inside a scattering sample onto a target plane. So far, it has proved challenging to non-invasively characterize the scattered optical wavefront inside a disordered medium. Here, we present a non-invasive scattering compensation method, termed F-SHARP, which allows us to measure the scattered electric-field point spread function (E-field PSF) in three dimensions. Knowledge of the phase and amplitude of the E-field PSF makes it possible to optically cancel sample turbulence. We demonstrate the imaging capabilities of this technique on a variety of samples and notably through vertebrate brains and across thinned skull in vivo.Weniger anzeigen
Hydrogenases are redox enzymes that catalyze the conversion of protons and molecular hydrogen (H2). Based on the composition of the active site cofactor, the monometallic [Fe]-hydrogenase is distinguished from the bimetallic [NiFe]- or [FeFe]-hydrogenase. The latter has been reported with particularly high turnover activities for both H2 release and H2 oxidation, notably at neutral pH, ambient temperatures, and negligible electric overpotential. Due to these properties, [FeFe]-hydrogenase represents the “gold standard” in enzymatic hydrogen turnover. Understanding hydrogenase chemistry is crucial for the design of transition metal complexes that serve as potentially sustainable proton reduction or H2 oxidation catalysts, e.g., in electrolytic devices or fuel cells. However, even 20 years after the crystal structures of [FeFe]-hydrogenase have been published, several aspects of biological hydrogen turnover are heatedly discussed. In this perspective, we give an overview on how the diversity of naturally occurring and artificially prepared, semisynthetic [FeFe]-hydrogenases deepens our understanding of hydrogenase chemistry. In parallel, we cover recent results from biophysical techniques that go beyond the scope of conventional X-ray diffraction, EPR, and FTIR spectroscopy. Taking into account both proton transfer and electron transfer as well as the notorious sensitivity of [FeFe]-hydrogenase toward carbon monoxide, the discussion further touches upon the molecular proceedings of biological hydrogen turnover.Weniger anzeigen
As a result of its indirect bandgap, emitting photons from silicon in an efficient way remains challenging. Silicon light emitters that can be integrated seamlessly on a CMOS platform have been demonstrated; however, none satisfies an ensemble of key requirements such as a small footprint, room-temperature operation at low voltages, and emission of narrow and polarized lines with a high spectral power density in the near-infrared range. Here, we present an all-silicon electrically driven light emitting diode that consists of an inversely tapered half-ellipsoidal silicon photonic resonator containing a p–n junction used to excite whispering gallery modes (WGMs) inside the resonator. Under low voltage operation at room temperature, such a photonic silicon light-emitting diode exhibits a band-edge emission (900–1300 nm) with a wall-plug efficiency of 10−4. The emitted spectrum is amplified in multiple WGMs and shows peaks that are polarized and have linewidths Δλ as narrow as 0.33 nm and spectral power densities as high as 8 mW cm−2 nm−1. Considering its small footprint of ∼1 µm and remarkable emission characteristics, this silicon light source constitutes a significant step ahead toward fully integrated on-chip silicon photonics.Weniger anzeigen
Electronic relaxation of atomic Kr below and above the 1s ionization threshold is investigated experimentally using hard x-ray photoelectron spectroscopy. The experimental results are interpreted with the aid of relativistic Dirac-Fock calculations. The 1s orbital core-hole lifetime is extracted and the satellite's structures accompanying the photoelectron main line are assigned. Auger spectra recorded below and above the K edge are also investigated. In particular, the Auger cascade originating from vacancies of different origin in the L shell is analyzed in great detail. Competition between radiative KL versus nonradiative KLL Auger emission is emphasized.Weniger anzeigen
The adaptive resolution simulation (AdResS) technique couples regions with different molecular resolutions and allows the exchange of molecules between different regions in an adaptive fashion. The latest development of the technique allows to abruptly couple the atomistically resolved region with a region of non‐interacting point‐like particles. The abrupt set‐up is derived having in mind the idea of the atomistically resolved region as an open system embedded in a large reservoir at a given macroscopic state. In this work, starting from the idea of open systems, the authors derive thermodynamic relations for AdResS which justify conceptually and numerically the claim of AdResS as a technique for simulating open systems. In particular, the relation between the chemical potential of the AdResS set‐up and that of its reference fully atomistic simulation is derived. The implication of this result is that the grand potential of AdResS can be explicitly written and thus, from a statistical mechanics point of view, the atomistically resolved region of AdResS can be identified with a well‐defined open system.Weniger anzeigen
A binary liquid near its consolute point exhibits critical fluctuations of local composition and a diverging correlation length. The method of choice to calculate critical points in the phase diagram is a finite-size scaling analysis, based on a sequence of simulations with widely different system sizes. Modern, massively parallel hardware facilitates that instead cubic sub-systems of one large simulation are used. Here, this alternative is applied to a symmetric binary liquid at critical composition and different routes to the critical temperature are compared: 1) fitting critical divergences of the composition structure factor, 2) scaling of fluctuations in sub-volumes, and 3) applying the cumulant intersection criterion to sub-systems. For the last route, two difficulties arise: sub-volumes are open systems, for which no precise estimate of the critical Binder cumulant Uc is available. Second, the boundaries of the simulation box interfere with the sub-volumes, which is resolved here by a two-parameter finite-size scaling. The implied modification to the data analysis restores the common intersection point, yielding Uc=0.201 +/- 0.001, universal for cubic Ising-like systems with free boundaries. Confluent corrections to scaling, which arise for small sub-system sizes, are quantified and the data are compatible with the universal correction exponent omega approximate to 0.83.Weniger anzeigen
Modern methods of simulating molecular systems are based on the mathematical theory of Markov operators with a focus on autonomous equilibrated systems. However, non‐autonomous physical systems or non‐autonomous simulation processes are becoming more and more important. A representation of non‐autonomous Markov jump processes is presented as autonomous Markov chains on space‐time. Augmenting the spatial information of the embedded Markov chain by the temporal information of the associated jump times, the so‐called augmented jump chain is derived. The augmented jump chain inherits the sparseness of the infinitesimal generator of the original process and therefore provides a useful tool for studying time‐dependent dynamics even in high dimensions. Furthermore, possible generalizations and applications to the computation of committor functions and coherent sets in the non‐autonomous setting are discussed. After deriving the theoretical foundations, the concepts with a proof‐of‐concept Galerkin discretization of the transfer operator of the augmented jump chain applied to simple examples are illustrated.Weniger anzeigen
We compute stress drops from P and S phase spectra for 534 earthquakes in the source region of the 2014 MW8.1 Iquique megathrust earthquake in the northern Chilean subduction zone. An empirical Green's function based method is applied to suitable event pairs selected by template matching of eight years of continuous waveform data. We evaluate the parameters involved in the stress drop estimation, consider the effect of the local velocity structure and apply an empirical linear relation between P and S phase related geometry factors (k values). Data redundancy produced by multiple empirical Green's function and the combination of P and S phase spectra leads to a substantial reduction of uncertainty and robust stress drop estimates. The resulting stress drop values show a well‐defined log‐normal distribution with a median value of 4.36 MPa; most values range between 0.1 and 100 MPa. There is no evidence for systematic large scale lateral variations of stress drop. A detailed analysis reveals several regions of increased median stress drop, an increase with distance to the interface, but no consistent increase with depth. This suggests that fault regime and fault strength have a stronger impact on the stress drop behavior than absolute stresses. Interestingly, we find a weak time‐dependence of the median stress drop, with an increase immediately before the April 1, 2014 MW8.1 Iquique mainshock, a continuous reduction thereafter and a subsequent recovery to average values. Additionally, the data set indicates a relatively strong dependence of stress drop on magnitude which extends over the entire analyzed magnitude range.Weniger anzeigen
Asymmetric dimethylarginine (ADMA) is a cardiac biomarker in humans, symmetric dimethylarginine (SDMA) a renal biomarker in humans, cats, and dogs. The purpose of this prospective study was to investigate if measuring serum ADMA and SDMA concentrations via ELISA allows detection of cardiac disease in horses in a routine laboratory setting. In this context, reference values in horses were established. Animals, materials, and methods
Seventy-eight horses with no known medical history were compared to 23 horses with confirmed structural cardiac disease with/or without arrhythmias. Horses underwent physical examination, electrocardiography, echocardiography and venous blood sampling and were staged based on the severity of cardiac disease from 0 to II. Asymmetric dimethylarginine and SDMA were measured via ELISA and crosschecked using liquid chromatograph triple quadrupole mass spectrometry. Reference intervals with 90th percent confidence intervals were evaluated and standard software was used to test for significant differences in ADMA, SDMA, and the l-arginine/ADMA ratio between groups. Results
The reference ranges were 1.7–3.8 μmol/L and 0.3–0.8 μmol/L for ADMA and SDMA, respectively. Serum ADMA was higher in horses with heart disease compared to healthy horses (p < 0.01) and highest in horses with stage II heart disease (p = 0.02). The l-Arginine/ADMA ratio was significantly higher in healthy animals than those with cardiac disease (p = 0.001). Conclusions
Reference values for serum ADMA and SDMA using ELISA methods are presented in horses. This study confirms the association between heart disease and increased serum ADMA concentration as well as a decreased l-Arginine/ADMA ratio in horses.Weniger anzeigen
Seismic activity below the standard seismogenic zone is difficult to investigate because the geological records of such earthquakes, pseudotachylytes, are typically reacted and/or deformed. Here, we describe unusually pristine pseudotachylytes in lower-crustal granulites from the Lofoten Archipelago, northern Norway. The pseudotachylytes have essentially the same mineralogical composition as their host (mainly plagioclase, alkali feldspar, orthopyroxene) and contain microstructures indicative of rapid cooling, i.e., feldspar microlites and spherulites and "cauliflower" garnets. Mylonites are absent, both in the wall rocks and among the pseudotachylyte clasts. The absence of features recording precursory ductile deformation rules out several commonly invoked mechanisms for triggering earthquakes in the lower crust, including thermal runaway, plastic instabilities, and downward propagation of seismic slip from the brittle to the ductile part of a fault. The anhydrous mineralogy of host and pseudotachylytes excludes dehydration-induced embrittlement. In the absence of such weakening mechanisms, stress levels in the lower crust must have been transiently high.Weniger anzeigen
The airflow in dairy barns is affected by many factors, such as the barn's geometry, weather conditions, configurations of the openings, cows acting as heat sources, flow obstacles, etc. Computational fluids dynamics (CFD) has the advantages of providing detailed airflow information and allowing fully-controlled boundary conditions, and therefore is widely used in livestock building research. However, due to the limited computing power, numerous animals are difficult to be designed in detail. Consequently, there is the need to develop and use smart numerical models in order to reduce the computing power needed while at the same time keeping a comparable level of accuracy.
In this work the porous medium modeling is considered to solve this problem using Ansys Fluent. A comparison between an animal occupied zone (AOZ) filled with randomly arranged 22 simplified cows' geometry model (CM) and the porous medium model (PMM) of it, was made. Anisotropic behavior of the PMM was implemented in the porous modeling to account for turbulence influences. The velocity at the inlet of the domain has been varied from 0.1 m s(-1) to 3 in s(-1) and the temperature difference between the animals and the incoming air was set at 20 K. Leading to Richardson numbers Ri corresponding to the three types of heat transfer convection, i.e. natural, mixed and forced convection. It has been found that the difference between two models (the cow geometry model and the PMM) was around 2% for the pressure drop and less than 6% for the convective heat transfer. Further the usefulness of parametrized PMM with a velocity adaptive pressure drop and heat transfer coefficient is shown by velocity field validation of an on-farm measurement.Weniger anzeigen
In the past two decades, most of the steps in a macromolecular crystallography experiment have undergone tremendous development with respect to speed, feasibility and increase of throughput. The part of the experimental workflow that is still a bottleneck, despite significant efforts, involves the manipulation and harvesting of the crystals for the diffraction experiment. Here, a novel low-cost device is presented that functions as a cover for 96-well crystallization plates. This device enables access to the individual experiments one at a time by its movable parts, while minimizing evaporation of all other experiments of the plate. In initial tests, drops of many typically used crystallization cocktails could be successfully protected for up to 6 h. Therefore, the manipulation and harvesting of crystals is straightforward for the experimenter, enabling significantly higher throughput. This is useful for many macromolecular crystallography experiments, especially multi-crystal screening campaigns.Weniger anzeigen
Zwischen dem Artikel „Weiblichkeit“ und dem Artikel „Werk“ fehlt in den von Karlheinz Barck et al. herausgegebenen Ästhetischen Grundbegriffen eine „Welt“. Und im Reallexikon der deutschen Literaturwissenschaft gibt es zwar das „weltliche Spiel“, die „Weltliteratur“ und – direkt vor dem „Werbetext“ – das „Welttheater“, nicht aber die „Welt“ selbst, noch nicht einmal eine mögliche. Dieses Fehlen, die Lücke im Lexikon ästhetischer und literaturwissenschaftlicher Grundbegriffe, lässt sich als manifester Ausdruck eines epistemologischen Mangels lesen: In ihm begegnet einem gleichsam die sichtbare Leerstelle, die die kantische Erkenntniskritik in den Enzyklopädien der Moderne hinterlassen hat, indem sie das Ganze der Welt ins unerreichbare Außerhalb der menschlichen Erkenntnisfähigkeit rückte. Dass nicht erst seit Kants Antinomien der reinen Vernunft in diese begriffliche Leerstelle die Metapher tritt, hat Hans Blumenberg zum Fundament seiner Metaphorologie gemacht. Um den Ausgangspunkt dieser Metaphorologie bei der Frage „Was ist die Welt?” kreisen zahlreiche der in diesem Band versammelten Texte...Weniger anzeigen
Ionizing radiation damage to DNA plays a fundamental role in cancer therapy. X-ray photoelectron-spectroscopy (XPS) allows simultaneous irradiation and damage monitoring. Although water radiolysis is essential for radiation damage, all previous XPS studies were performed in vacuum. Here we present near-ambient-pressure XPS xperiments to directly measure DNA damage under water atmosphere. They permit in-situ monitoring of the effects of radicals on fully hydrated double-stranded DNA. The results allow us to distinguish direct damage, by photons and secondary low-energy electrons (LEE), from damage by hydroxyl radicals or hydration induced modifications of damage pathways. The exposure of dry DNA to x-rays leads to strand-breaks at the sugar-phosphate backbone, while deoxyribose and nucleobases are less affected. In contrast, a strong increase of DNA damage is observed in water, where OH-radicals are produced. In consequence, base damage and base release become predominant, even though the number of strand-breaks increases further.Weniger anzeigen
Background: The average treatment effect of antidepressants in major depression was found to be about 2 points on the 17-item Hamilton Depression Rating Scale, which lies below clinical relevance. Here, we searched for evidence of a relevant treatment effect heterogeneity that could justify the usage of antidepressants despite their low average treatment effect.
Methods: Bayesian meta-analysis of 169 randomized, controlled trials including 58,687 patients. We considered the effect sizes log variability ratio (lnVR) and log coefficient of variation ratio (lnCVR) to analyze the difference in variability of active and placebo response. We used Bayesian random-effects meta-analyses (REMA) for lnVR and lnCVR and fitted a random-effects meta-regression (REMR) model to estimate the treatment effect variability between antidepressants and placebo.
Results: The variability ratio was found to be very close to 1 in the best fitting models (REMR: 95% highest density interval (HDI) [0.98, 1.02], REMA: 95% HDI [1.00, 1.02]). The between-study standard deviation tau under the REMA with respect to lnVR was found to be low (95% HDI [0.00, 0.02]). Simulations showed that a large treatment effect heterogeneity is only compatible with the data if a strong correlation between placebo response and individual treatment effect is assumed.
Conclusions: The published data from RCTs on antidepressants for the treatment of major depression is compatible with a near-constant treatment effect. Although it is impossible to rule out a substantial treatment effect heterogeneity, its existence seems rather unlikely. Since the average treatment effect of antidepressants falls short of clinical relevance, the current prescribing practice should be re-evaluated.Weniger anzeigen
Cu oxides catalyze the electrochemical carbon dioxide reduction reaction (CO2RR) to hydrocarbons and oxygenates with favorable selectivity. Among them, the shape-controlled Cu oxide cubes have been most widely studied. In contrast, we report on novel 2-dimensional (2D) Cu(II) oxide nanosheet (CuO NS) catalysts with high C2+ products, selectivities (> 400mAcm(-2)) in gas diffusion electrodes (GDE) at industrially relevant currents and neutral pH. Under applied bias, the (001)-orientated CuO NS slowly evolve into highly branched, metallic Cu-0 dendrites that appear as a general dominant morphology under electrolyte flow conditions, as attested by operando X-ray absorption spectroscopy and in situ electrochemical transmission electron microscopy (TEM). Millisecond-resolved differential electrochemical mass spectrometry (DEMS) track a previously unavailable set of product onset potentials. While the close mechanistic relation between CO and C2H4 was thereby confirmed, the DEMS data help uncover an unexpected mechanistic link between CH4 and ethanol. We demonstrate evidence that adsorbed methyl species, *CH3, serve as common intermediates of both CH3H and CH3CH2OH and possibly of other CH3-R products via a previously overlooked pathway at (110) steps adjacent to (100) terraces at larger overpotentials. Our mechanistic conclusions challenge and refine our current mechanistic understanding of the CO2 electrolysis on Cu catalysts. Copper oxides (CuO) can selectively catalyze the electrochemical reduction of CO2 to hydrocarbons and oxygenates. Here, the authors study the activity and morphological evolution of 2D CuO nanosheets under applied electrode potentials to conclude the primacy of dendritic shapes and involvement of a new coupling pathway.Weniger anzeigen
Students' cheating is a serious problem: It undermines the chance to adequately promote, support, and evaluate them. To explain cheating behavior, research seldom focuses on perceived teachers' characteristics. Thus, we investigate the relationship between students' cheating behavior and an important teacher characteristic, individual reference norm orientation (IRNO; i.e., the tendency to evaluate students based on their performance development over time). We examined cheating on written exams, on homework, and in oral exams among N = 601 students (64.2% girls; M (age) = 16.07 years) in N = 31 language classes. Results from doubly manifest multi-level analyses showed that, on the classroom level, cheating on written exams and on homework occurred less frequently the more the classroom of students perceived their teachers as having an IRNO. We found no further evidence for other cheating factors or student characteristics. This supports the idea that teacher characteristics are associated with some forms of students' cheating behavior.Weniger anzeigen
The Armenian highlands encompasses rugged and environmentally diverse landscapes and is characterized by a mosaic of distinct ecological niches and large temperature gradients. Strong seasonal fluctuations in resource availability along topographic gradients likely prompted Pleistocene hominin groups to adapt by adjusting their mobility strategies. However, the role that elevated landscapes played in hunter-gatherer settlement systems during the Late Pleistocene (Middle Palaeolithic [MP]) remains poorly understood. At 1640 m above sea level, the MP site of Kalavan 2 (Armenia) is ideally positioned for testing hypotheses involving elevation-dependent seasonal mobility and subsistence strategies. Renewed excavations at Kalavan 2 exposed three main occupation horizons and ten additional low densities lithic and faunal assemblages. The results provide a new chronological, stratigraphical, and paleoenvironmental framework for hominin behaviors between ca. 60 to 45 ka. The evidence presented suggests that the stratified occupations at Kalavan 2 locale were repeated ephemerally most likely related to hunting in a high-elevation within the mountainous steppe landscape.Weniger anzeigen
Qubit reset is a key task in the operation of quantum devices which, for many quantum hardware platforms, presently limits device clock speed. While it is known that coupling the qubit to an ancilla on demand allows for the fastest qubit reset, the limits on reset accuracy and speed due to the choice of ancilla have not yet been identified-despite the great flexibility in device design for most quantum hardware platforms. Here, we derive bounds on qubit reset in terms of maximum fidelity and minimum time, assuming control over the qubit and no control over the ancilla. For two-level ancillas, we find a provably time-optimal protocol which consists of purity exchange between qubit and ancilla brought into resonance. The globally minimal time can only be realized for specific choices of coupling and control which we identify. When increasing the size of the ancilla Hilbert space, the maximally achievable fidelity increases, whereas the reset time remains constant. Our results translate into device design principles for realizing, in a given quantum architecture, the fastest and most accurate protocol for qubit reset.Weniger anzeigen
Complex interactive test items are becoming more widely used in assessments. Being computer-administered, assessments using interactive items allow logging time-stamped action sequences. These sequences pose a rich source of information that may facilitate investigating how examinees approach an item and arrive at their given response. There is a rich body of research leveraging action sequence data for investigating examinees' behavior. However, the associated timing data have been considered mainly on the item-level, if at all. Considering timing data on the action-level in addition to action sequences, however, has vast potential to support a more fine-grained assessment of examinees' behavior. We provide an approach that jointly considers action sequences and action-level times for identifying common response processes. In doing so, we integrate tools from clickstream analyses and graph-modeled data clustering with psychometrics. In our approach, we (a) provide similarity measures that are based on both actions and the associated action-level timing data and (b) subsequently employ cluster edge deletion for identifying homogeneous, interpretable, well-separated groups of action patterns, each describing a common response process. Guidelines on how to apply the approach are provided. The approach and its utility are illustrated on a complex problem-solving item from PIAAC 2012.Weniger anzeigen