Magnetism and metallicity in moiré transition metal dichalcogenides.

The ability to control the properties of twisted bilayer transition metal dichalcogenides in situ makes them an ideal platform for investigating the interplay of strong correlations and geometric frustration. Of particular interest are the low energy scales, which make it possible to experimentally access both temperature and magnetic fields that are of the order of the bandwidth or the correlation scale. In this manuscript, we analyze the moiré Hubbard model, believed to describe the low energy physics of an important subclass of the twisted bilayer compounds. We establish its magnetic and the metal-insulator phase diagram for the full range of magnetic fields up to the fully spin-polarized state. We find a rich phase diagram including fully and partially polarized insulating and metallic phases of which we determine the interplay of magnetic order, Zeeman-field, and metallicity, and make connection to recent experiments.

Intertwined spin, charge, and pair correlations in the two-dimensional Hubbard model in the thermodynamic limit.

The high-temperature superconducting cuprates are governed by intertwined spin, charge, and superconducting orders. While various state-of-the-art numerical methods have demonstrated that these phases also manifest themselves in doped Hubbard models, they differ on which is the actual ground state. Finite-cluster methods typically indicate that stripe order dominates, while embedded quantum-cluster methods, which access the thermodynamic limit by treating long-range correlations with a dynamical mean field, conclude that superconductivity does. Here, we report the observation of fluctuating spin and charge stripes in the doped single-band Hubbard model using a quantum Monte Carlo dynamical cluster approximation (DCA) method. By resolving both the fluctuating spin and charge orders using DCA, we demonstrate that they survive in the doped Hubbard model in the thermodynamic limit. This discovery also provides an opportunity to study the influence of fluctuating stripe correlations on the model's pairing correlations within a unified numerical framework. Using this approach, we also find evidence for pair-density-wave correlations whose strength is correlated with that of the stripes.

Targeted transcriptomics reveals signatures of large-scale independent origins and concerted regulation of effector genes in Radopholus similis.

The burrowing nematode, Radopholus similis, is an economically important plant-parasitic nematode that inflicts damage and yield loss to a wide range of crops. This migratory endoparasite is widely distributed in warmer regions and causes extensive destruction to the root systems of important food crops (e.g., citrus, banana). Despite the economic importance of this nematode, little is known about the repertoire of effectors owned by this species. Here we combined spatially and temporally resolved next-generation sequencing datasets of R. similis to select a list of candidates for the identification of effector genes for this species. We confirmed spatial expression of transcripts of 30 new candidate effectors within the esophageal glands of R. similis by in situ hybridization, revealing a large number of pioneer genes specific to this nematode. We identify a gland promoter motif specifically associated with the subventral glands (named Rs-SUG box), a putative hallmark of spatial and concerted regulation of these effectors. Nematode transcriptome analyses confirmed the expression of these effectors during the interaction with the host, with a large number of pioneer genes being especially abundant. Our data revealed that R. similis holds a diverse and emergent repertoire of effectors, which has been shaped by various evolutionary events, including neofunctionalization, horizontal gene transfer, and possibly by de novo gene birth. In addition, we also report the first GH62 gene so far discovered for any metazoan and putatively acquired by lateral gene transfer from a bacterial donor. Considering the economic damage caused by R. similis, this information provides valuable data to elucidate the mode of parasitism of this nematode.

Two-site study on performances of a commercially available MALDI-TOF MS-based assay for the detection of colistin resistance in Escherichia coli.

Colistin is a last resort drug for the treatment of multiple drug-resistant (MDR) Gram-negative bacterial infections. Rapid methods to detect resistance are highly desirable. Here, we evaluated the performance of a commercially available MALDI-TOF MS-based assay for colistin resistance testing in Escherichia coli at two different sites. Ninety clinical E. coli isolates were provided by France and tested in Germany and UK using a MALDI-TOF MS-based colistin resistance assay. Lipid A molecules of the bacterial cell membrane were extracted using the MBT Lipid Xtract Kit™ (RUO; Bruker Daltonics, Germany). Spectra acquisition and evaluation were performed by the MBT HT LipidART Module of MBT Compass HT (RUO; Bruker Daltonics) on a MALDI Biotyper® sirius system (Bruker Daltonics) in negative ion mode. Phenotypic colistin resistance was determined by broth microdilution (MICRONAUT MIC-Strip Colistin, Bruker Daltonics) and used as a reference. Comparing the results of the MALDI-TOF MS-based colistin resistance assay with the data of the phenotypic reference method for the UK, sensitivity and specificity for the detection of colistin resistance were 97.1% (33/34) and 96.4% (53/55), respectively. Germany showed 97.1% (33/34) sensitivity and 100% (55/55) specificity for the detection of colistin resistance by MALDI-TOF MS. Applying the MBT Lipid Xtract™ Kit in combination with MALDI-TOF MS and dedicated software showed excellent performances for E. coli. Analytical and clinical validation studies must be performed to demonstrate the performance of the method as a diagnostic tool.

Serious Games and Gamification: Health Care Workers' Experience, Attitudes, and Knowledge.

OBJECTIVE: With the rapid advancement of digital technology due to COVID-19, the health care field is embracing the use of digital technologies for learning, which presents an opportunity for teaching methods such as serious games to be developed and improved. Technology offers more options for these educational approaches. The goal of this study was to assess health care workers' experiences, attitudes, and knowledge regarding serious games in training. METHODS: The convenience sample consisted of 223 participants from the specialties of internal medicine and psychiatry who responded to questions regarding sociodemographic data, experience, attitudes, and knowledge regarding serious games. This study used an ordinal regression model to analyze the relationship between knowledge, attitudes, and experiences and the idea or wish to implement serious games. RESULTS: The majority of healthcare workers were not familiar with serious games or gamification. The results show gender and age differences regarding familiarity and willingness to use serious games. With increasing age, the respondents preferred conventional and traditional learning methods to playful teaching elements; younger generations were significantly more motivated than older generations when envisioning using elements of serious games in the future. CONCLUSIONS: The COVID-19 pandemic has encouraged the use of new technologies and digitalization. This study describes positive attitudes toward serious games, mainly in younger people working in health care. Serious games present an opportunity to develop new approaches for postgraduate medical teachings and continuing medical education.

ART─An Amino Radical Transfer Strategy for C(sp2)-C(sp3) Coupling Reactions, Enabled by Dual Photo/Nickel Catalysis.

Introducing the novel concept of amino radical transfer (ART) enables the use of easily accessible and commercially available alkyl boronic esters as cross-coupling partners for aryl halides in dual photoredox/nickel catalysis mediated by visible light. Activation of otherwise photochemically innocent boronic esters by radicals generated from primary or secondary alkylamines gives rise to an outstanding functional group tolerance in a mild, fast, and air-stable reaction. As shown in more than 50 examples including unprotected alcohols, amines, and carboxylic acids, this reaction allows quick access to relevant scaffolds for organic synthesis and medicinal chemistry. In comparison with existing methods for C(sp2)-C(sp3) couplings an extraordinary generality could be realized via the ART concept, employing a single set of optimized reaction conditions. Due to its selectivity, the transformation can also be used for late-stage functionalization, as demonstrated with three exemplary syntheses of drug molecules. Furthermore, the successful one-to-one scalability of this reaction up to gram scale without the necessity of any further precautions or flow systems is demonstrated.

Observing the Rosensweig instability of a quantum ferrofluid.

Ferrofluids exhibit unusual hydrodynamic effects owing to the magnetic nature of their constituents. As magnetization increases, a classical ferrofluid undergoes a Rosensweig instability and creates self-organized, ordered surface structures or droplet crystals. Quantum ferrofluids such as Bose-Einstein condensates with strong dipolar interactions also display superfluidity. The field of dipolar quantum gases is motivated by the search for new phases of matter that break continuous symmetries. The simultaneous breaking of continuous symmetries such as the phase invariance in a superfluid state and the translational symmetry in a crystal provides the basis for these new states of matter. However, interaction-induced crystallization in a superfluid has not yet been observed. Here we use in situ imaging to directly observe the spontaneous transition from an unstructured superfluid to an ordered arrangement of droplets in an atomic dysprosium Bose-Einstein condensate. By using a Feshbach resonance to control the interparticle interactions, we induce a finite-wavelength instability and observe discrete droplets in a triangular structure, the number of which grows as the number of atoms increases. We find that these structured states are surprisingly long-lived and observe hysteretic behaviour, which is typical for a crystallization process and in close analogy to the Rosensweig instability. Our system exhibits both superfluidity and, as we show here, spontaneous translational symmetry breaking. Although our observations do not probe superfluidity in the structured states, if the droplets establish a common phase via weak links, then our system is a very good candidate for a supersolid ground state.

Di-tert-butyldiphosphatetrahedrane as a Source of 1,2-Diphosphacyclobutadiene Ligands.

Reactions of di-tert-butyldiphosphatetrahedrane (1) with cycloocta-1,5-diene- or anthracene-stabilised metalate anions of iron and cobalt consistently afford complexes of the rarely encountered 1,2-diphosphacyclobutadiene ligand, which have previously been very challenging synthetic targets. The subsequent reactivity of 1,2-diphosphacyclobutadiene cobaltates toward various electrophiles has also been investigated and is compared to reactions of related 1,3-diphosphacyclobutadiene complexes. The results highlight the distinct reactivity of such isomeric species, showing that the 1,2-isomers can act as precursors for previously unknown triphospholium ligands. The electronic structures of the new complexes were investigated by several methods, including NMR, EPR and Mößbauer spectroscopies as well as quantum chemical calculations.

Re-targeting of a plant defense protease by a cyst nematode effector.

Plants mount defense responses during pathogen attacks, and robust host defense suppression by pathogen effector proteins is essential for infection success. 4E02 is an effector of the sugar beet cyst nematode Heterodera schachtii. Arabidopsis thaliana lines expressing the effector-coding sequence showed altered expression levels of defense response genes, as well as higher susceptibility to both the biotroph H. schachtii and the necrotroph Botrytis cinerea, indicating a potential suppression of defenses by 4E02. Yeast two-hybrid analyses showed that 4E02 targets A. thaliana vacuolar papain-like cysteine protease (PLCP) 'Responsive to Dehydration 21A' (RD21A), which has been shown to function in the plant defense response. Activity-based protein profiling analyses documented that the in planta presence of 4E02 does not impede enzymatic activity of RD21A. Instead, 4E02 mediates a re-localization of this protease from the vacuole to the nucleus and cytoplasm, which is likely to prevent the protease from performing its defense function and at the same time, brings it in contact with novel substrates. Yeast two-hybrid analyses showed that RD21A interacts with multiple host proteins including enzymes involved in defense responses as well as carbohydrate metabolism. In support of a role in carbohydrate metabolism of RD21A after its effector-mediated re-localization, we observed cell wall compositional changes in 4E02 expressing A. thaliana lines. Collectively, our study shows that 4E02 removes RD21A from its defense-inducing pathway and repurposes this enzyme by targeting the active protease to different cell compartments.

A new esophageal gland transcriptome reveals signatures of large scale de novo effector birth in the root lesion nematode Pratylenchus penetrans.

BACKGROUND: The root lesion nematode Pratylenchus penetrans is a migratory plant-parasitic nematode responsible for economically important losses in a wide number of crops. Despite the importance of P. penetrans, the molecular mechanisms employed by this nematode to promote virulence remain largely unknown. RESULTS: Here we generated a new and comprehensive esophageal glands-specific transcriptome library for P. penetrans. In-depth analysis of this transcriptome enabled a robust identification of a catalogue of 30 new candidate effector genes, which were experimentally validated in the esophageal glands by in situ hybridization. We further validated the expression of a multifaceted network of candidate effectors during the interaction with different plants. To advance our understanding of the "effectorome" of P. penetrans, we adopted a phylogenetic approach and compared the expanded effector repertoire of P. penetrans to the genome/transcriptome of other nematode species with similar or contrasting parasitism strategies. Our data allowed us to infer plausible evolutionary histories that shaped the effector repertoire of P. penetrans, as well as other close and distant plant-parasitic nematodes. Two remarkable trends were apparent: 1) large scale effector birth in the Pratylenchidae in general and P. penetrans in particular, and 2) large scale effector death in sedentary (endo) plant-parasitic nematodes. CONCLUSIONS: Our study doubles the number of validated Pratylenchus penetrans effectors reported in the literature. The dramatic effector gene gain in P. penetrans could be related to the remarkable ability of this nematode to parasitize a large number of plants. Our data provide valuable insights into nematode parasitism and contribute towards basic understating of the adaptation of P. penetrans and other root lesion nematodes to specific host plants.

Tight regulation of FOXO1 is essential for maintenance of B-cell precursor acute lymphoblastic leukemia.

The FOXO1 transcription factor plays an essential role in the regulation of proliferation and survival programs at early stages of B-cell differentiation. Here, we show that tightly regulated FOXO1 activity is essential for maintenance of B-cell precursor acute lymphoblastic leukemia (BCP-ALL). Genetic and pharmacological inactivation of FOXO1 in BCP-ALL cell lines produced a strong antileukemic effect associated with CCND3 downregulation. Moreover, we demonstrated that CCND3 expression is critical for BCP-ALL survival and that overexpression of CCND3 protected BCP-ALL cell lines from growth arrest and apoptosis induced by FOXO1 inactivation. Most importantly, pharmacological inhibition of FOXO1 showed antileukemia activity on several primary, patient-derived, pediatric ALL xenografts with effective leukemia reduction in the hematopoietic, lymphoid, and central nervous system organ compartments, ultimately leading to prolonged survival without leukemia reoccurrence in a preclinical in vivo model of BCP-ALL. These results suggest that repression of FOXO1 might be a feasible approach for the treatment of BCP-ALL.

Heterogeneous Olefin Hydrogenation Enabled by a Highly-Reduced Nickel(-II) Catalyst Precursor.

Invited for the cover of this issue is the group of Robert Wolf at the University of Regensburg and colleagues at the University of Hamburg. The image depicts the hydrogenation of triphenylethylene. Read the full text of the article at 10.1002/chem.201905537.

Heterogeneous Olefin Hydrogenation Enabled by a Highly-Reduced Nickel(-II) Catalyst Precursor.

The hydrogenation of olefins, styrenes, enoates, imines, and sterically hindered tri-substituted olefins was accomplished using the pre-catalyst dilithiumbis(cycloocta-1,5-diene)nickelate(-II) (1). The mild conditions tolerate hydroxyl, halide, ester, and lactone functionalities. Mechanistic studies, including reaction progress analyses, poisoning experiments, and multinuclear NMR monitoring, indicate that a heterotopic (nickel nanoparticle) catalyst is in operation.

Low-Valence Anionic α-Diimine Iron Complexes: Synthesis, Characterization, and Catalytic Hydroboration Studies.

The synthesis of rare anionic heteroleptic and homoleptic α-diimine iron complexes is described. Heteroleptic BIAN (bis(aryl)iminoacenaphthene) complexes 1-[K([18]c-6)(thf)0.5] and 2-[K([18]c-6)(thf)2] were synthesized by reduction of the [(BIAN)FeBr2] precursor complex using stoichiometric amounts of potassium graphite in the presence of the corresponding olefin. The electronic structure of these paramagnetic species was investigated by numerous spectroscopic analyses (NMR, EPR, 57Fe Mössbauer, UV-vis), magnetic measurements (Evans NMR method, SQUID), and theoretical techniques (DFT, CASSCF). Whereas anion 1 is a low-spin complex, anion 2 consists of an intermediate-spin Fe(III) center. Both complexes are efficient precatalysts for the hydroboration of carbonyl compounds under mild reaction conditions. The reaction of bis(anthracene) ferrate(1-) gave the homoleptic BIAN complex 3-[K([18]c-6)(thf)], which is less catalytically active. The electronic structure was elucidated with the same techniques as described for complexes 1-[K([18]c-6)(thf)0.5] and 2-[K([18]c-6)(thf)2] and revealed an Fe(II) species in a quartet ground state.

Lateral silicon oxide/gold interfaces enhance the rate of electrochemical hydrogen evolution reaction in alkaline media.

The production of solar hydrogen with a silicon based water splitting device is a promising future technology, and silicon-based metal-insulator-semiconductor (MIS) electrodes have been proposed as suitable architectures for efficient photocathodes based on the electronic properties of the MIS structures and the catalytic properties of the metals. In this paper, we demonstrate that the interfaces between the metal and oxide of laterally patterned MIS electrodes may strongly enhance the catalytic activity of the electrode compared to bulk metal surfaces. The employed electrodes consist of well-defined, large-area arrays of gold structures of various mesoscopic sizes embedded in a silicon oxide support on silicon. We demonstrate that the activity of these electrodes for hydrogen evolution reaction (HER) increases with an increase in gold/silicon oxide boundary length in both acidic and alkaline media, although the enhancement of the HER rate in alkaline electrolytes is considerably larger than in acidic electrolytes. Electrodes with the largest interfacial length of gold/silicon oxide exhibited a 10-times larger HER rate in alkaline electrolytes than those with the smallest interfacial length. The data suggest that at the metal/silicon oxide boundaries, alkaline HER is enhanced through a bifunctional mechanism, which we tentatively relate to the laterally structured electrode geometry and to positive charges present in silicon oxide: Both properties change locally the interfacial electric field at the gold/silicon oxide boundary, which, in turn, facilitates a faster transport of hydroxide ions away from the electrode/electrolyte interface in alkaline solution. This mechanism boosts the alkaline HER activity of p-type silicon based photoelectrodes close to their HER activity in acidic electrolytes.

Amine-Borane Dehydrogenation and Transfer Hydrogenation Catalyzed by α-Diimine Cobaltates.

Anionic α-diimine cobalt complexes, such as [K(thf)1.5 {(Dipp BIAN)Co(η4 -cod)}] (1; Dipp=2,6-diisopropylphenyl, cod=1,5-cyclooctadiene), catalyze the dehydrogenation of several amine-boranes. Based on the excellent catalytic properties, an especially effective transfer hydrogenation protocol for challenging olefins, imines, and N-heteroarenes was developed. NH3 BH3 was used as a dihydrogen surrogate, which transferred up to two equivalents of H2 per NH3 BH3 . Detailed spectroscopic and mechanistic studies are presented, which document the rate determination by acidic protons in the amine-borane.

Influence of wheel rim width on rolling resistance and off-road speed in cross-country mountain biking.

The rim width of cross-country mountain bike wheel sets has increased in recent years, but the effect of this increase on performance remains unknown. The aim of this study was to analyse the influence of rim width on rolling resistance and off-road speed. We compared 3 tubeless wheel sets: 25 mm inner width as baseline, 30 mm width with the same tyre stiffness, and 30 mm width with the same tyre pressure. Three riders conducted 75 rolling resistance tests for each wheel set on a cross-country course. We determined rolling resistance using the virtual elevation method and calculated off-road speeds for flat and uphill conditions using a mathematical model. Baseline rolling resistance (Cr) was 0.0298, 90% CI [0.0286, 0.0310], which decreased by 1.4%, [0.7, 2.2] with the wider rim and the same tyre stiffness and increased by 0.9%, [0.1, 1.6] with the wider rim and the same tyre pressure. The corresponding effects on off-road speed were most likely trivial (0.0% to 0.7% faster and 0.1% to 0.6% slower, respectively). Because the effect of rim width on off-road speed seems negligible, athletes should choose the rim width that offers the best bike handling and should experiment with low tyre pressures.

[3+2] Fragmentation of a Pentaphosphido Ligand by Cyanide.

The activation of white phosphorus (P4 ) by transition-metal complexes has been studied for several decades, but the functionalization and release of the resulting (organo)phosphorus ligands has rarely been achieved. Herein we describe the formation of rare diphosphan-1-ide anions from a P5 ligand by treatment with cyanide. Cobalt diorganopentaphosphido complexes have been synthesized by a stepwise reaction sequence involving a low-valent diimine cobalt complex, white phosphorus, and diorganochlorophosphanes. The reactions of the complexes with tetraalkylammonium or potassium cyanide afford a cyclotriphosphido cobaltate anion 5 and 1-cyanodiphosphan-1-ide anions [R2 PPCN]- (6-R). The molecular structure of a related product 7 suggests a novel reaction mechanism, where coordination of the cyanide anion to the cobalt center induces a ligand rearrangement. This is followed by nucleophilic attack of a second cyanide anion at a phosphorus atom and release of the P2 fragment.

Differential Associations Among PTSD and Complex PTSD Symptoms and Traumatic Experiences and Postmigration Difficulties in a Culturally Diverse Refugee Sample.

Forced migration is one of the major challenges currently facing the international community. Many refugees have been affected by traumatic experiences at home and during their flight, putting them at a heightened risk of developing trauma-related disorders. The new version of the International Classification of Diseases (ICD-11) introduced two sibling disorders, posttraumatic stress disorder (PTSD) and complex PTSD (CPTSD). So far, little is known about risk and protective factors in refugees that are specifically associated with the disturbances in self-organization (DSO) characteristic of CPTSD. In this study, we aimed to investigate the association between PTSD and DSO symptoms and traumatic experiences, postmigration difficulties, and social support in a culturally diverse sample of refugees who resettled in Switzerland. A total of 94 refugees (85.1% male; M age = 31.60 years, SD = 10.14, range: 18-61 years) participated in this study. Trained assessors performed either guided questionnaire assessments or structured interviews. In our advice- and help-seeking sample, 32.9% of individuals suffered from PTSD and 21.3% from CPTSD. After controlling for potential gender differences, we found positive associations between PTSD symptoms and trauma exposure, ß = .22, as well as between DSO symptoms and postmigration living difficulties, ß = .42, and lack of social support, ß = .22. Our findings support the notion that it is highly important to consider differential associations among PTSD and DSO symptoms and risk and protective factors to gain a deeper understanding of the trauma-related problems refugees face.

Predicting biathlon shooting performance using machine learning.

Shooting in biathlon competitions substantially influences final rankings, but the predictability of hits and misses is unknown. The aims of the current study were A) to explore factors influencing biathlon shooting performance and B) to predict future hits and misses. We explored data from 118,300 shots from 4 seasons and trained various machine learning models before predicting 34,340 future shots (in the subsequent season). A) Lower hit rates were discovered in the sprint and pursuit disciplines compared to individual and mass start (P < 0.01, h = 0.14), in standing compared to prone shooting (P < 0.01, h = 0.15) and in the 1st prone and 5th standing shot (P < 0.01, h = 0.08 and P < 0.05, h = 0.05). B) A tree-based boosting model predicted future shots with an area under the ROC curve of 0.62, 95% CI [0.60, 0.63], slightly outperforming a simple logistic regression model and an artificial neural network (P < 0.01). The dominant predictor was an athlete's preceding mode-specific hit rate, but a high degree of randomness persisted, which complex models could not substantially reduce. Athletes should focus on overall mode-specific hit rates which epitomise shooting skill, while other influences seem minor.