Homoleptic Low-Valent Polyazides of Group 14 Elements

First examples of coordinatively unsaturated, homoleptic azido complexes of low-valent group 14 elements are reported. A simple strategy uses low-valent precursors, ionic azide transfer reagents and bulky cations to obtain salt-like compounds containing E(N3)3- of Ge(II)/Sn(II) which are fully characterised, including XRD. Remarkably, these compounds are kinetically stable at r.t. and isolable in sub-gram quantities

X-ray absorption spectroscopy systematics at the tungsten L-edge

A series of mononuclear six-coordinate tungsten compounds spanning formal oxidation states from 0 to +VI, largely in a ligand environment of inert chloride and/or phosphine, has been interrogated by tungsten L-edge X-ray absorption spectroscopy. The L-edge spectra of this compound set, comprised of [W<sup>0</sup>(PMe<sub>3</sub>)<sub>6</sub>], [W<sup>II</sup>Cl<sub>2</sub>(PMePh<sub>2</sub>)<sub>4</sub>], [W<sup>III</sup>Cl<sub>2</sub>(dppe)<sub>2</sub>][PF<sub>6</sub>] (dppe = 1,2-bis(diphenylphosphino)ethane), [W<sup>IV</sup>Cl<sub>4</sub>(PMePh<sub>2</sub>)<sub>2</sub>], [W<sup>V</sup>(NPh)Cl<sub>3</sub>(PMe<sub>3</sub>)<sub>2</sub>], and [W<sup>VI</sup>Cl<sub>6</sub>] correlate with formal oxidation state and have usefulness as references for the interpretation of the L-edge spectra of tungsten compounds with redox-active ligands and ambiguous electronic structure descriptions. The utility of these spectra arises from the combined correlation of the estimated branching ratio (EBR) of the L<sub>3,2</sub>-edges and the L<sub>1</sub> rising-edge energy with metal Z<sub>eff</sub>, thereby permitting an assessment of effective metal oxidation state. An application of these reference spectra is illustrated by their use as backdrop for the L-edge X-ray absorption spectra of [W<sup>IV</sup>(mdt)<sub>2</sub>(CO)<sub>2</sub>] and [W<sup>IV</sup>(mdt)<sub>2</sub>(CN)<sub>2</sub>]<sup>2–</sup> (mdt<sup>2–</sup> = 1,2-dimethylethene-1,2-dithiolate), which shows that both compounds are effectively W<sup>IV</sup> species. Use of metal L-edge XAS to assess a compound of uncertain formulation requires: 1) Placement of that data within the context of spectra offered by unambiguous calibrant compounds, preferably with the same coordination number and similar metal ligand distances. Such spectra assist in defining upper and/or lower limits for metal Z<sub>eff</sub> in the species of interest; 2) Evaluation of that data in conjunction with information from other physical methods, especially ligand K-edge XAS; 3) Increased care in interpretation if strong π-acceptor ligands, particularly CO, or π-donor ligands are present. The electron-withdrawing/donating nature of these ligand types, combined with relatively short metal-ligand distances, exaggerate the difference between formal oxidation state and metal Z<sub>eff</sub> or, as in the case of [W<sup>IV</sup>(mdt)<sub>2</sub>(CO)<sub>2</sub>], add other subtlety by modulating the redox level of other ligands in the coordination sphere

Regression spline bivariate probit models: A practical approach to testing for exogeneity

Bivariate probit models can deal with a problem usually known as endogeneity. This issue is likely to arise in observational studies when confounders are unobserved. We are concerned with testing the hypothesis of exogeneity (or absence of endogeneity) when using regression spline recursive and sample selection bivariate probit models. Likelihood ratio and gradient tests are discussed in this context and their empirical properties investigated and compared with those of the Lagrange multiplier and Wald tests through a Monte Carlo study. The tests are illustrated using two datasets in which the hypothesis of exogeneity needs to be tested

The polymycovirus-mediated growth enhancement of the entomopathogenic fungus Beauveria bassiana is dependent on carbon and nitrogen metabolism

Polymycoviridae is a growing family of mycoviruses whose members typically have non-conventional capsids and multi-segmented, double-stranded (ds) RNA genomes. Beauveria bassiana polymycovirus (BbPmV) 1 is known to enhance the growth and virulence of its fungal host, the entomopathogenic ascomycete and popular biological control agent B. bassiana. Here we report the complete sequence of BbPmV-3, which has six genomic dsRNA segments. Phylogenetic analysis of RNA-dependent RNA polymerase (RdRp) protein sequences revealed that BbPmV-3 is closely related to the partially sequenced BbPmV-2 but not BbPmV-1. Nevertheless, both BbPmV-3 and BbPmV-1 have similar effects on their respective host isolates ATHUM 4946 and EABb 92/11-Dm, affecting pigmentation, sporulation, and radial growth. Production of conidia and radial growth are significantly enhanced in virus-infected isolates as compared to virus-free isogenic lines on Czapek-Dox complete and minimal media that contain sucrose and sodium nitrate. However, this polymycovirus-mediated effect on growth is dependent on the carbon and nitrogen sources available to the host fungus. Both BbPmV-3 and BbPmV-1 increase growth of ATHUM 4946 and EABb 92/11-Dm when sucrose is replaced by lactose, trehalose, glucose, or glycerol, while the effect is reversed on maltose and fructose. Similarly, both BbPmV-3 and BbPmV-1 decrease growth of ATHUM 4946 and EABb 92/11-Dm when sodium nitrate is replaced by sodium nitrite, potassium nitrate, or ammonium nitrate. In conclusion, the effects of polymycoviruses on B. bassiana are at least partially mediated via its metabolic pathways

Capturing accelerometer outputs in healthy volunteers under normal and simulated-pathological conditions using ML classifiers

Wearable devices offer a possible solution for acquiring objective measurements of physical activity. Most current algorithms are derived using data from healthy volunteers. It is unclear whether such algorithms are suitable in specific clinical scenarios, such as when an individual has altered gait. We hypothesized that algorithms trained on healthy population will result in less accurate results when tested in individuals with altered gait. We further hypothesized that algorithms trained on simulated-pathological gait would prove better at classifying abnormal activity.We studied healthy volunteers to assess whether activity classification accuracy differed for those with healthy and simulated-pathological conditions. Healthy participants (n=30) were recruited from the University of Leeds to perform nine predefined activities under healthy and simulated-pathological conditions. Activities were captured using a wrist-worn MOX accelerometer (Maastricht Instruments, NL). Data were analyzed based on the Activity-Recognition-Chain process. We trained a Neural-Network, Random-Forests, k-Nearest-Neighbors (k-NN), Support-Vector-Machines (SVM) and Naive Bayes models to classify activity. Algorithms were trained four times; once with 'healthy' data, and once with 'simulated-pathological data' for each of activity-type and activity-task classification. In activity-type instances, the SVM provided the best results; the accuracy was 98.4% when the algorithm was trained and then tested with unseen data from the same group of healthy individuals. Accuracy dropped to 52.8% when tested on simulated-pathological data. When the model was retrained with simulated-pathological data, prediction accuracy for the corresponding test set was 96.7%. Algorithms developed on healthy data are less accurate for pathological conditions. When evaluating pathological conditions, classifier algorithms developed using data from a target sub-population can restore accuracy to above 95%.Clinical Relevance - This method remotely establishes health-related data of objective outcome measures of activities of daily living

One-year efficacy and safety of single or one to three weekly injections of hylan G-F 20 for knee osteoarthritis: a systematic literature review and meta-analysis

The aim of this study was to evaluate the long-term efficacy and safety of single or 1–3 weekly injections of hylan G-F 20 at 1 year following the first injection for knee osteoarthritis (OA). Searches were conducted in PubMed/MEDLINE, Embase, and CENTRAL and included relevant conference proceedings (January 1, 1995–August 17, 2020). Randomized controlled trials (RCTs), non-randomized trials, and observational studies investigating 1-year efficacy and safety of 1–3 weekly injections or single hylan G-F 20 injection for knee OA were included. Primary outcomes were WOMAC pain, physical function, and stiffness. Meta-analyses of RCTs and non-randomized studies were conducted separately. Our search identified 24 eligible studies. Hylan G-F 20, in the meta-analyses of RCTs, showed statistically significant improvement in WOMAC pain (SMCC − 0.98, 95% CI − 1.50, − 0.46), physical function (SMCC − 1.05, 95% CI − 1.28, − 0.83), and stiffness (SMCC − 1.07, 95% CI −1.28, −0.86). Improvement was also seen for VAS pain, SF-36 MCS (mental component summary), and SF-36 PCS (physical component summary). Analyses of non-randomized studies showed similar efficacy estimates. There were no significant differences in efficacy based on injection schedule, nor between RCT and non-randomized studies. Rates of adverse events (AEs) were low for most types of AEs. Hylan G-F 20 (either as single or 1–3 weekly injections) showed improvement in 1-year efficacy outcomes in comparison to baseline and was generally well tolerated. While further research will inform the medical field regarding viscosupplementation treatment options for knee OA, these findings show that hylan G-F 20 at both frequencies/dosages are efficacious and generally well tolerated for long-term use

Magnetic racetrack memory: from physics to the cusp of applications within a decade

Racetrack memory (RTM) is a novel spintronic memory-storage technology that has the potential to overcome fundamental constraints of existing memory and storage devices. It is unique in that its core differentiating feature is the movement of data, which is composed of magnetic domain walls (DWs), by short current pulses. This enables more data to be stored per unit area compared to any other current technologies. On the one hand, RTM has the potential for mass data storage with unlimited endurance using considerably less energy than today's technologies. On the other hand, RTM promises an ultrafast nonvolatile memory competitive with static random access memory (SRAM) but with a much smaller footprint. During the last decade, the discovery of novel physical mechanisms to operate RTM has led to a major enhancement in the efficiency with which nanoscopic, chiral DWs can be manipulated. New materials and artificially atomically engineered thin-film structures have been found to increase the speed and lower the threshold current with which the data bits can be manipulated. With these recent developments, RTM has attracted the attention of the computer architecture community that has evaluated the use of RTM at various levels in the memory stack. Recent studies advocate RTM as a promising compromise between, on the one hand, power-hungry, volatile memories and, on the other hand, slow, nonvolatile storage. By optimizing the memory subsystem, significant performance improvements can be achieved, enabling a new era of cache, graphical processing units, and high capacity memory devices. In this article, we provide an overview of the major developments of RTM technology from both the physics and computer architecture perspectives over the past decade. We identify the remaining challenges and give an outlook on its future

Advancing Brain Research through Surface-Enhanced Raman Spectroscopy (SERS):Current Applications and Future Prospects

Surface-enhanced Raman spectroscopy (SERS) has recently emerged as a potent analytical technique with significant potential in the field of brain research. This review explores the applications and innovations of SERS in understanding the pathophysiological basis and diagnosis of brain disorders. SERS holds significant advantages over conventional Raman spectroscopy, particularly in terms of sensitivity and stability. The integration of label-free SERS presents promising opportunities for the rapid, reliable, and non-invasive diagnosis of brain-associated diseases, particularly when combined with advanced computational methods such as machine learning. SERS has potential to deepen our understanding of brain diseases, enhancing diagnosis, monitoring, and therapeutic interventions. Such advancements could significantly enhance the accuracy of clinical diagnosis and further our understanding of brain-related processes and diseases. This review assesses the utility of SERS in diagnosing and understanding the pathophysiological basis of brain disorders such as Alzheimer’s and Parkinson’s diseases, stroke, and brain cancer. Recent technological advances in SERS instrumentation and techniques are discussed, including innovations in nanoparticle design, substrate materials, and imaging technologies. We also explore prospects and emerging trends, offering insights into new technologies, while also addressing various challenges and limitations associated with SERS in brain research

Heusler-based synthetic antiferrimagnets

Antiferromagnet spintronic devices eliminate or mitigate long-range dipolar fields, thereby promising ultrafast operation. For spin transport electronics, one of the most successful strategies is the creation of metallic synthetic antiferromagnets, which, to date, have largely been formed from transition metals and their alloys. Here, we show that synthetic antiferrimagnetic sandwiches can be formed using exchange coupling spacer layers composed of atomically ordered RuAl layers and ultrathin, perpendicularly magnetized, tetragonal ferrimagnetic Heusler layers. Chemically ordered RuAl layers can both be grown on top of a Heusler layer and allow for the growth of ordered Heusler layers deposited on top of it that are as thin as one unit cell. The RuAl spacer layer gives rise to a thickness-dependent oscillatory interlayer coupling with an oscillation period of ~1.1 nm. The observation of ultrathin ordered synthetic antiferrimagnets substantially expands the family of synthetic antiferromagnets and magnetic compounds for spintronic technologies