BloodSpot 3.0: a database of gene and protein expression data in normal and malignant haematopoiesis.

BloodSpot is a specialised database integrating gene expression data from acute myeloid leukaemia (AML) patients related to blood cell development and maturation. The database and interface has helped numerous researchers and clinicians to quickly get an overview of gene expression patterns in healthy and malignant haematopoiesis. Here, we present an update to our framework that includes protein expression data of sorted single cells. With this update we also introduce datasets broadly spanning age groups, which many users have requested, with particular interest for researchers studying paediatric leukaemias. The backend of the database has been rewritten and migrated to a cloud-based environment to accommodate the growth, and provide a better user-experience for our many international users. Users can now enjoy faster transfer speeds and a more responsive interface. In conclusion, the continuing popularity of the database and emergence of new data modalities has prompted us to rewrite and futureproof the back-end, including paediatric centric views, as well as single cell protein data, allowing us to keep the database updated and relevant for the years to come. The database is freely available at www.bloodspot.eu.

Emergence of Weyl fermions by ferrimagnetism in a noncentrosymmetric magnetic Weyl semimetal.

Condensed matter physics has often provided a platform for investigating the interplay between particles and fields in cases that have not been observed in high-energy physics. Here, using angle-resolved photoemission spectroscopy, we provide an example of this by visualizing the electronic structure of a noncentrosymmetric magnetic Weyl semimetal candidate NdAlSi in both the paramagnetic and ferrimagnetic states. We observe surface Fermi arcs and bulk Weyl fermion dispersion as well as the emergence of new Weyl fermions in the ferrimagnetic state. Our results establish NdAlSi as a magnetic Weyl semimetal and provide an experimental observation of ferrimagnetic regulation of Weyl fermions in condensed matter.

In Situ Exfoliation Method of Large-Area 2D Materials.

2D materials provide a rich platform to study novel physical phenomena arising from quantum confinement of charge carriers. Many of these phenomena are discovered by surface sensitive techniques, such as photoemission spectroscopy, that work in ultra-high vacuum (UHV). Success in experimental studies of 2D materials, however, inherently relies on producing adsorbate-free, large-area, high-quality samples. The method that yields 2D materials of highest quality is mechanical exfoliation from bulk-grown samples. However, as this technique is traditionally performed in a dedicated environment, the transfer of samples into vacuum requires surface cleaning that might diminish the quality of the samples. In this article, a simple method for in situ exfoliation directly in UHV is reported, which yields large-area, single-layered films. Multiple metallic and semiconducting transition metal dichalcogenides are exfoliated in situ onto Au, Ag, and Ge. The exfoliated flakes are found to be of sub-millimeter size with excellent crystallinity and purity, as supported by angle-resolved photoemission spectroscopy, atomic force microscopy, and low-energy electron diffraction. The approach is well-suited for air-sensitive 2D materials, enabling the study of a new suite of electronic properties. In addition, the exfoliation of surface alloys and the possibility of controlling the substrate-2D material twist angle is demonstrated.

Energetics of formation and stability in high pressure steam of barium lanthanide cobaltite double perovskites.

This study concerns energetics of formation and the stability in high water partial pressure of BaLnCo2O6-δ, (Ln = La, Pr, Nd, and Gd) (BLnC) and BaGd1-xLaxCo2O6-δ, where x = 0.2, 0.5, and 0.7 (BGLC) double perovskite cobaltites. Those materials are extensively studied due to their potential applications as a positrode in electrochemical devices. Therefore, their stability under such conditions is a key issue. All investigated materials are thermodynamically stable relative to binary oxides and exhibit strongly exothermic enthalpies of formation. Moreover, BaGd0.3La0.7Co2O6-δ and BaGd0.8La0.2Co2O6-δ remain the main perovskite structure up to 3 bars of water vapor at 400 °C. At higher steam pressure, reaching 10 bar at 300 °C, the partial decomposition to constituent oxides and hydroxides was observed. The BGLC compounds exhibit higher negative formation enthalpies in comparison to single-Ln compositions, which does not translate into higher chemical stability under high steam pressures since the BLnC series retained the main perovskite structure at higher temperatures as well as in higher water vapor pressures.

Efficient low-density grating setup for monochromatization of XUV ultrafast light sources.

Ultrafast light sources have become an indispensable tool to access and understand transient phenomenon in material science. However, a simple and easy-to-implement method for harmonic selection, with high transmission efficiency and pulse duration conservation, is still a challenge. Here we showcase and compare two approaches for selecting the desired harmonic from a high harmonic generation source while achieving the above goals. The first approach is the combination of extreme ultraviolet spherical mirrors with transmission filters and the second approach uses a normal-incidence spherical grating. Both solutions target time- and angle-resolved photoemission spectroscopy with photon energies in the 10-20 eV range but are relevant for other experimental techniques as well. The two approaches for harmonic selection are characterized in terms of focusing quality, photon flux, and temporal broadening. It is demonstrated that a focusing grating is able to provide much higher transmission as compared to the mirror+filter approach (3.3 times higher for 10.8 eV and 12.9 times higher for 18.1 eV), with only a slight temporal broadening (6.8% increase) and a somewhat larger spot size (∼30% increase). Overall, our study establishes an experimental perspective on the trade-off between a single grating normal incidence monochromator design and the use of filters. As such, it provides a basis for selecting the most appropriate approach in various fields where an easy-to-implement harmonic selection from high harmonic generation is needed.

Structural properties of mixed conductor Ba1-xGd1-yLax+yCo2O6-δ.

Ba1-xGd1-yLax+yCo2O6-δ (BGLC) compositions with large compositional ranges of Ba, Gd, and La have been characterised with respect to phase compositions, structure, and thermal and chemical expansion. The results show a system with large compositional flexibility, enabling tuning of functional properties and thermal and chemical expansion. We show anisotropic chemical expansion and detailed refinements of emerging phases as La is substituted for Ba and Gd. The dominating phase is the double perovskite structure Pmmm, which is A-site ordered along the c-axes and with O vacancy ordering along the b-axis in the Ln-layer. Phases emerging when substituting La for Ba are orthorhombic Ba-deficient Pbnm and cubic LaCoO3-based R3̄c. When La is almost completely substituted for Gd, the material can be stabilised in Pmmm, or cubic Pm3̄m, depending on thermal and atmospheric history. We list thermal expansion coefficients for x = 0-0.3, y = 0.2.

A narrow bandwidth extreme ultra-violet light source for time- and angle-resolved photoemission spectroscopy.

Here, we present a high repetition rate, narrow bandwidth, extreme ultraviolet photon source for time- and angle-resolved photoemission spectroscopy. The narrow bandwidth pulses Δ E = 9 , 14 , and 18 meV for photon energies h ν = 10.8 , 18.1 , and 25.3 eV are generated through high harmonic generation using ultra-violet drive pulses with relatively long pulse lengths (461 fs). The high harmonic generation setup employs an annular drive beam in tight focusing geometry at a repetition rate of 250 kHz. Photon energy selection is provided by a series of selectable multilayer bandpass mirrors and thin film filters, thus avoiding any time broadening introduced by single grating monochromators. A two stage optical-parametric amplifier provides < 100 fs tunable pump pulses from 0.65 µm to 9 µm. The narrow bandwidth performance of the light source is demonstrated through angle-resolved photoemission measurements on a series of quantum materials, including high-temperature superconductor Bi-2212, WSe2, and graphene.

Promoting Selective Generation of Formic Acid from CO2 Using Mn(bpy)(CO)3Br as Electrocatalyst and Triethylamine/Isopropanol as Additives.

Urgent solutions are needed to efficiently convert the greenhouse gas CO2 into higher-value products. In this work, fac-Mn(bpy)(CO)3Br (bpy = 2,2'-bipyridine) is employed as electrocatalyst in reductive CO2 conversion. It is shown that product selectivity can be shifted from CO toward HCOOH using appropriate additives, i.e., Et3N along with iPrOH. A crucial aspect of the strategy is to outrun the dimer-generating parent-child reaction involving fac-Mn(bpy)(CO)3Br and [Mn(bpy)(CO)3]- and instead produce the Mn hydride intermediate. Preferentially, this is done at the first reduction wave to enable formation of HCOOH at an overpotential as low as 260 mV and with faradaic efficiency of 59 ± 1%. The latter may be increased to 71 ± 3% at an overpotential of 560 mV, using 2 M concentrations of both Et3N and iPrOH. The nature of the amine additive is crucial for product selectivity, as the faradaic efficiency for HCOOH formation decreases to 13 ± 4% if Et3N is replaced with Et2NH. The origin of this difference lies in the ability of Et3N/iPrOH to establish an equilibrium solution of isopropyl carbonate and CO2, while with Et2NH/iPrOH, formation of the diethylcarbamic acid is favored. According to density-functional theory calculations, CO2 in the former case can take part favorably in the catalytic cycle, while this is less opportune in the latter case because of the CO2-to-carbamic acid conversion. This work presents a straightforward procedure for electrochemical reduction of CO2 to HCOOH by combining an easily synthesized manganese catalyst with commercially available additives.

Imaging Ultrafast Dynamical Diffraction Wave Fronts in Strained Si with Coherent X Rays.

Dynamical diffraction effects in thin single crystals produce highly monochromatic parallel x-ray beams with a mutual separation of a few microns and a time delay of a few femtoseconds-the so-called echoes. This ultrafast diffraction effect is used at X-Ray Free Electron Lasers in self-seeding schemes to improve beam monochromaticity. Here, we present a coherent x-ray imaging measurement of echoes from Si crystals and demonstrate that a small surface strain can be used to tune their temporal delay. These results represent a first step toward the ambitious goal of strain tailoring new x-ray optics and, conversely, open up the possibility of using ultrafast dynamical diffraction effects to study strain in materials.

Experimental and computational characterization of phase transitions in CsB3H8.

Metal hydroborates are versatile materials with interesting properties related to energy storage and cation conductivity. The hydrides containing B3H8- (triborane, or octahydrotriborate) ions have been at the center of attention for some time as reversible intermediates in the decomposition of BH4- (3BH4-↔ B3H8- + 2H2), and as conducting media in electrolytes based on boron-hydride cage clusters. We report here the first observation of two phase transitions in CsB3H8 prior to its decomposition above 230 °C. The previously reported orthorhombic room temperature phase (here named α-CsB3H8) with the space group Ama2 changes into a new phase with the space group Pnma at 73 °C (here named ß-CsB3H8), and then into a face-centered cubic phase, here named γ-CsB3H8, at 88 °C. These phases are not stable at room temperature thus requiring in situ measurements for their characterization. The phase transitions and decomposition pathway of CsB3H8 were studied with in situ synchrotron powder X-ray diffraction (SR-PXD), in situ and ex situ vibrational spectroscopies (Raman and FTIR), and differential-scanning calorimetry combined with thermo-gravimetric analysis (DSC-TGA). The structure determination was validated by vibrational spectroscopy analysis and modeling of the periodic structures by density functional methods. In γ-CsB3H8, a significant disorder in B3H8- positions and orientations was found which can potentially benefit cation conducting properties through the paddle mechanism.

Double Perovskite Cobaltites Integrated in a Monolithic and Noble Metal-Free Photoelectrochemical Device for Efficient Water Splitting.

Water photoelectrolysis has the potential to produce renewable hydrogen fuel, therefore addressing the intermittent nature of sunlight. Herein, a monolithic, photovoltaic (PV)-assisted water electrolysis device of minimal engineering and of low (in the µg range) noble-metal-free catalysts loading is presented for unassisted water splitting in alkaline media. An efficient double perovskite cobaltite catalyst, originally developed for high-temperature proton-conducting ceramic electrolyzers, possesses high activity for the oxygen evolution reaction in alkaline media at room temperatures too. Ba1-xGd1-yLax+yCo2O6-δ (BGLC) is combined with a NiMo cathode, and a solar-to-hydrogen efficiency of 6.6% in 1.0 M NaOH, under 1 sun simulated illumination for 71 h, is demonstrated. This work highlights how readily available earth-abundant materials and established PV methods can achieve high performance and stable and monolithic photoelectrolysis devices with potential for full-scale applications.

Are Amines the Holy Grail for Facilitating CO2 Reduction?

The selective and efficient reduction of carbon dioxide represents a key solution to producing non-fossil-fuel-based feedstocks for the chemical industry, while alleviating the increasing atmospheric concentration of this greenhouse gas. A variety of catalytic methods for the CO2 reduction reaction (CO2 RR) have been developed, including hydrogenations and electrochemical or photochemical reductions. For many of the most significant breakthroughs reported in the last decade, we realized that amines or closely related functional groups play a critical role for such transformations, and in several cases, are directly associated with the catalyst as a pendant group. Amines play multiple roles, such as CO2 trapping agents, proton shuttles, electron donors, or facilitators of CO2 reductions through formamide derivatives. In this Viewpoint, we compile some of these recent findings, and discuss their significance in a broader context in an attempt to provide guidelines for the design of new catalysts with enhanced activity and selectivity.

Elucidating the Effects of the Composition on Hydrogen Sorption in TiVZrNbHf-Based High-Entropy Alloys.

A number of high-entropy alloys (HEAs) in the TiVZrNbHf system have been synthesized by arc melting and systematically evaluated for their hydrogen sorption characteristics. A total of 21 alloys with varying elemental compositions were investigated, and 17 of them form body-centered-cubic (bcc) solid solutions in the as-cast state. A total of 15 alloys form either face-centered-cubic (fcc) or body-centered-tetragonal (bct) hydrides after exposure to gaseous hydrogen with hydrogen per metal ratios (H/M) as high as 2.0. Linear trends are observed between the volumetric expansion per metal atom [(V/Z)fcc/bct - (V/Z)bcc/hcp]/(V/Z)bcc/hcp with the valence electron concentration and average Pauling electronegativity (χp) of the alloys. However, no correlation was observed between the atomic size mismatch, δ, and any investigated hydrogen sorption property such as the maximum storage capacity or onset temperature for hydrogen release.

Synthesis and characterization of Magnesium-Iron-Cobalt complex hydrides.

The formation, structure and deuterium desorption properties of Mg2FexCo(1-x)Dy (0 ≤ x ≤ 1 and 5 ≤ y ≤ 6) complex hydrides were investigated. The synthesis was carried out by reactive ball milling, using a mixture of powders of the parent elements in D2 atmosphere. The formation of quaternary deuterides was identified from Rietveld refinements of powder X-Ray diffraction and powder neutron diffraction patterns, and from infrared attenuated total reflectance analysis. It was observed that the crystal structure of deuterides depends on the transition metal fraction. For Co-rich compositions, i.e. up to x = 0.1, hydrides have the tetragonal distorted CaF2-type structure (space group P4/nmm) of Mg2CoD5 at room temperature. For Fe-rich compositions, i.e. x ≥ 0.5, a cubic hydride is observed, with the same K2PtCl6-type structure (space group Fm[Formula: see text]m) as Mg2FeD6 and as Mg2CoD5 at high temperatures. For x = 0.3, both the cubic and the tetragonal deuterides are detected. Differential scanning calorimetry coupled with thermogravimetric and temperature programmed desorption analyses show rather similar deuterium desorption properties for all samples, without significant changes as a function of composition. Finally, hydrogen sorption experiments performed for Mg2Fe0.5Co0.5H5.5 at 30 bar of H2 and 673 K showed reversible reactions, with good kinetic for both absorption and desorption of hydrogen.

Dynamics of porous and amorphous magnesium borohydride to understand solid state Mg-ion-conductors.

Rechargeable solid-state magnesium batteries are considered for high energy density storage and usage in mobile applications as well as to store energy from intermittent energy sources, triggering intense research for suitable electrode and electrolyte materials. Recently, magnesium borohydride, Mg(BH4)2, was found to be an effective precursor for solid-state Mg-ion conductors. During the mechanochemical synthesis of these Mg-ion conductors, amorphous Mg(BH4)2 is typically formed and it was postulated that this amorphous phase promotes the conductivity. Here, electrochemical impedance spectroscopy of as-received γ-Mg(BH4)2 and ball milled, amorphous Mg(BH4)2 confirmed that the conductivity of the latter is ~2 orders of magnitude higher than in as-received γ-Mg(BH4)2 at 353 K. Pair distribution function (PDF) analysis of the local structure shows striking similarities up to a length scale of 5.1 Å, suggesting similar conduction pathways in both the crystalline and amorphous sample. Up to 12.27 Å the PDF indicates that a 3D net of interpenetrating channels might still be present in the amorphous phase although less ordered compared to the as-received γ-phase. However, quasi elastic neutron scattering experiments (QENS) were used to study the rotational mobility of the [BH4] units, revealing a much larger fraction of activated [BH4] rotations in amorphous Mg(BH4)2. These findings suggest that the conduction process in amorphous Mg(BH4)2 is supported by stronger rotational mobility, which is proposed to be the so-called "paddle-wheel" mechanism.

Pseudo-ternary LiBH4·LiCl·P2S5 system as structurally disordered bulk electrolyte for all-solid-state lithium batteries.

The properties of the mixed system LiBH4-LiCl-P2S5 are studied with respect to all-solid-state batteries. The studied material undergoes an amorphization upon heating above 60 °C, accompanied with increased Li+ conductivity beneficial for battery electrolyte applications. The measured ionic conductivity is ∼10-3 S cm-1 at room temperature with an activation energy of 0.40(2) eV after amorphization. Structural analysis and characterization of the material suggest that BH4 groups and PS4 may belong to the same molecular structure, where Cl ions interplay to accommodate the structural unit. Thanks to its conductivity, ductility and electrochemical stability (up to 5 V, Au vs. Li+/Li), this new electrolyte is successfully tested in battery cells operated with a cathode material (layered TiS2, theo. capacity 239 mA h g-1) and Li anode resulting in 93% capacity retention (10 cycles) and notable cycling stability under the current density ∼12 mA g-1 (0.05C-rate) at 50 °C. Further advanced characterisation by means of operando synchrotron X-ray diffraction in transmission mode contributes explicitly to a better understanding of the (de)lithiation processes of solid-state battery electrodes operated at moderate temperatures.

Novel biomarkers for prediction of outcome in hip fracture patients-An exploratory study.

BACKGROUND: Little is known about the value of biomarkers for prognostication in hip fracture patients. The main objective of the present study was to assess if biomarkers add useful information to an existing risk score for prediction of 30-day mortality in patients suffering from out of hospital hip fractures. METHODS: In a prospective observational single centre study, association between plasma concentration of ninety-two biomarkers at admission and 30-day mortality was analysed using logistic regression adjusted for risk factors included in Nottingham Hip Fracture Score (NHFS). Biomarkers associated with the outcome in the adjusted analysis were further evaluated by calculating the net reclassification improvement (NRI) and the change in area under the receiver operating characteristics curve (AUC) relative to the NHFS. RESULTS: 997 patients were included. Sixty-two patients died within 30 days (6.2%). Eleven biomarkers were associated with 30-day mortality in adjusted analysis. Of these biomarkers Growth Differentiation Factor-15 (GDF-15) had NRI for the primary outcome (12.1%; 95% CI: 1.2-23.3) and Carbohydrate Antigen 125 (CA-125) improved the AUC relative to NHFS (improvement: 0.05; 95% CI: 0.01-0.10, P = .027). Both CA-125 and GDF-15 improved the AUC for a composite outcome of 30-day mortality and cardiovascular complications. CONCLUSIONS: Adding GDF-15 or CA-125 to the Nottingham Hip Fracture Score improves the discrimination with regard to predicting 30-day mortality and may help to identify a subgroup of hip fracture patients with a particularly poor prognosis. The value of these biomarkers should be explored in further studies to confirm clinical utility.

Ligand-Controlled Product Selectivity in Electrochemical Carbon Dioxide Reduction Using Manganese Bipyridine Catalysts.

Electrocatalysis is a promising tool for utilizing carbon dioxide as a feedstock in the chemical industry. However, controlling the selectivity for different CO2 reduction products remains a major challenge. We report a series of manganese carbonyl complexes with elaborated bipyridine or phenanthroline ligands that can reduce CO2 to either formic acid, if the ligand structure contains strategically positioned tertiary amines, or CO, if the amine groups are absent in the ligand or are placed far from the metal center. The amine-modified complexes are benchmarked to be among the most active catalysts for reducing CO2 to formic acid, with a maximum turnover frequency of up to 5500 s-1 at an overpotential of 630 mV. The conversion even works at overpotentials as low as 300 mV, although through an alternative mechanism. Mechanistically, the formation of a Mn-hydride species aided by in situ protonated amine groups was determined to be a key intermediate by cyclic voltammetry, 1H NMR, DFT calculations, and infrared spectroelectrochemistry.

Female rats release a trapped cagemate following shaping of the door opening response: Opening latency when the restrainer was baited with food, was empty, or contained a cagemate.

Research on pro-social rat behaviour is growing within the fields of comparative psychology and social neuroscience. However, much work remains on mapping important variables influencing this behaviour, and there is even disagreement on whether this behaviour is empathetically motivated and correctly labelled pro-social, or whether the behaviour is motivated by social contact. The present study used the helping behaviour paradigm where a rat can release a familiar cagemate from a restrainer. Prior to testing with a trapped cagemate, restrainer door opening was trained and baseline opening latencies when the restrainer was empty or baited with food were established. The findings show that the first-time release occurred sooner than in previous research and that rats used a previously demonstrated response to release the trapped cagemate. Further, rats opened the restrainer door more often and with shorter latencies when the restrainer contained a cagemate than when the restrainer was empty, but less often and with longer latencies than when the restrainer contained food. The test of whether illumination levels affect door-opening included in the study showed no effects.