ABX-type hybrid organic-inorganic structures have recently emerged as a new class of meltable materials. Here, by the use of phenylphosphonium derivatives as A cation, we study liquid- and glass-forming behavior of a new family of hybrid structures, (RPhP)[Mn(dca)] (R = Me, Et, Ph; dca = dicyanamide). These new compounds melt at 196-237 °C () and then vitrify upon cooling to room temperature, forming glasses.
View Article and Find Full Text PDFObjective: To report a 3-year follow-up from the FemoroAcetabular Impingement Trial, comparing arthroscopic surgery with physiotherapy in the management of femoroacetabular impingement (FAI) syndrome for the dual primary outcomes of radiographic hip osteoarthritis (OA) and patient-reported outcome measures of activities of daily living.
Methods: Two-group parallel, assessor-blinded, pragmatic randomised controlled trial across seven sites. 222 participants aged 18-60 years with FAI syndrome confirmed clinically and radiologically were randomised (1:1) to receive arthroscopic hip surgery (n=112) or physiotherapy (n=110).
Melt alloying, the process of melting a physical powder blend to create a homogeneous alloy, is widely used in materials processing. By carefully selecting the materials and their proportions, the physical properties of the resulting alloy can be precisely controlled. In this study, we investigate the possibility of utilizing melt alloying principles for meltable two-dimensional hybrid organic-inorganic perovskites (2D-HOIPs).
View Article and Find Full Text PDFWe report vibrationally resolved threshold photoelectron spectra of several sulfur-containing reactive intermediates. This includes the organosulfur radicals CHS, CHS, CHSH, CHS, and SH, which are relevant in atmospheric chemistry and in astrochemical settings. Due to the high reactivity, the radicals were prepared pyrolysis of (CH)S.
View Article and Find Full Text PDFBelow its Jahn-Teller transition temperature, , NaNiO has a monoclinic layered structure consisting of alternating layers of edge-sharing NaO and Jahn-Teller-distorted NiO octahedra. Above where NaNiO is rhombohedral, diffraction measurements show the absence of a cooperative Jahn-Teller distortion, accompanied by an increase in the unit cell volume. Using neutron total scattering, solid-state Nuclear Magnetic Resonance (NMR), and extended X-ray absorption fine structure (EXAFS) experiments as local probes of the structure we find direct evidence for a displacive, as opposed to order-disorder, Jahn-Teller transition at .
View Article and Find Full Text PDFTuning magnetic properties in layered van der Waals (vdW) materials has captured significant attention due to the efficient control of ground states by heterostructuring and external stimuli. Electron doping by electrostatic gating, interfacial charge transfer, and intercalation is particularly effective in manipulating the exchange and spin-orbit properties, resulting in a control of Curie temperature (T) and magnetic anisotropy. Here, an uncharted role of intercalation is discovered to generate magnetic frustration.
View Article and Find Full Text PDFSympatric species are often locally adapted to distinct microhabitats. However, temporal variation may cause local maladaptation and species boundary breakdown, especially during extreme climatic events leading to episodic selection. Repeated reciprocal transplants can reveal the interplay between short and long-term patterns of natural selection.
View Article and Find Full Text PDFWhile hybridization was viewed as a hindrance to adaptation and speciation by early evolutionary biologists, recent studies have demonstrated the importance of hybridization in facilitating evolutionary processes. However, it is still not well-known what role spatial and temporal variation in natural selection play in the maintenance of naturally occurring hybrid zones. To identify whether hybridization is adaptive between two closely related monkeyflower species, and , we performed repeated reciprocal transplants between natural hybrid and pure species' populations.
View Article and Find Full Text PDFAims: Ankle fractures are common, mainly affecting adults aged 50 years and over. To aid recovery, some patients are referred to physiotherapy, but referral patterns vary, likely due to uncertainty about the effectiveness of this supervised rehabilitation approach. To inform clinical practice, this study will evaluate the effectiveness of supervised versus self-directed rehabilitation in improving ankle function for older adults with ankle fractures.
View Article and Find Full Text PDFBackground: The TWO Study (Transplantation Without Overimmunosuppression) aimed to investigate a novel approach to regulatory T-cell (Treg) therapy in renal transplant patients, using a delayed infusion protocol at 6 mo posttransplant to promote a Treg-skewed lymphocyte repopulation after alemtuzumab induction. We hypothesized that this would allow safe weaning of immunosuppression to tacrolimus alone. The COVID-19 pandemic led to the suspension of alemtuzumab use, and therefore, we report the unique cohort of 7 patients who underwent the original randomized controlled trial protocol.
View Article and Find Full Text PDFPersistent central nervous system (CNS) immune dysregulation and consequent dysfunction of multiple neural cell types is central to the neurobiological underpinnings of a cognitive impairment syndrome that can occur following traditional cancer therapies or certain infections. Immunotherapies have revolutionized cancer care for many tumor types, but the potential long-term cognitive sequelae are incompletely understood. Here, we demonstrate in mouse models that chimeric antigen receptor (CAR) T cell therapy for both CNS and non-CNS cancers can impair cognitive function and induce a persistent CNS immune response characterized by white matter microglial reactivity and elevated cerebrospinal fluid (CSF) cytokines and chemokines.
View Article and Find Full Text PDFHybrid organic-inorganic perovskites (HOIPs) occupy a prominent position in the field of materials chemistry due to their attractive optoelectronic properties. While extensive work has been done on the crystalline materials over the past decades, the newly reported glasses formed from HOIPs open up a new avenue for perovskite research with their unique structures and functionalities. Melt-quenching is the predominant route to glass formation; however, the absence of a stable liquid state prior to thermal decomposition precludes this method for most HOIPs.
View Article and Find Full Text PDFThe atomistic structure of lithium nickelate (LiNiO), the parent compound of Ni-rich layered oxide cathodes for Li-ion batteries, continues to elude a comprehensive understanding. The common consensus is that the material exhibits local Jahn-Teller distortions that dynamically reorient, resulting in a time-averaged undistorted 3̅ structure. Through a combination of ab initio molecular dynamics (AIMD) simulations and variable-temperature X-ray diffraction (VT-XRD), we explore Jahn-Teller distortions in LiNiO as a function of temperature.
View Article and Find Full Text PDFBackground: Statisticians are fundamental in ensuring clinical research, including clinical trials, are conducted with quality, transparency, reproducibility and integrity. Good Clinical Practice (GCP) is an international quality standard for the conduct of clinical trials research. Statisticians are required to undertake training on GCP but existing training is generic and, crucially, does not cover statistical activities.
View Article and Find Full Text PDFVan Vleck modes describe all possible displacements of octahedrally coordinated ligands about a core atom. They are a useful analytical tool for analysing the distortion of octahedra, particularly for first-order Jahn-Teller distortions, but determination of the Van Vleck modes of an octahedron is complicated by the presence of angular distortion of the octahedron. This problem is most commonly resolved by calculating the bond distortion modes ( , ) along the bond axes of the octahedron, disregarding the angular distortion and losing information on the octahedral shear modes ( , and ) in the process.
View Article and Find Full Text PDFBackground: Chronic pain is a major challenge for some people after total knee replacement (TKR). The changing impact of this complication during the first post-operative year remains unclear. This analysis aimed to examine how physical activity and health-related quality of life (HRQoL) evolved over the first year after TKR for patients with and without post-operative chronic knee pain.
View Article and Find Full Text PDFPhys Chem Chem Phys
November 2023
The potential energy surfaces of pure methanol and mixed methanol-water pentamers have been explored using chirped pulse Fourier-transform microwave spectroscopy aided by calculations. Rotational constants, anharmonic corrections, dipole moments, and relative energies were calculated for different conformers. Predicted rotational transitions were then fit to experimental spectra from 10-18 GHz and the assignments were confirmed using double resonance experiments where feasible.
View Article and Find Full Text PDFAssessing the early use of video-assisted thoracoscopic surgery (VATS) or intrapleural enzyme therapy (IET) in pleural infection requires a phase III randomized controlled trial (RCT). To establish the feasibility of randomization in a surgery-versus-nonsurgery trial as well as the key outcome measures that are important to identify relevant patient-centered outcomes in a subsequent RCT. The MIST-3 (third Multicenter Intrapleural Sepsis Trial) was a prospective multicenter RCT involving eight U.
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