Spin-crossover assisted metallization of few-layer FePS3_3 at 1.45 GPa

Magnetic insulators in reduced dimension are the ideal model systems to study spin-crossover(SCO) induced cooperative behavior under pressure. Similar to the external perturbations like light illumination or temperature, external pressure may provide new pathway to accelerate giant lattice collapse,and subsequently Mott transition in van der Waals (vdW) materials with diminishing effect of the third dimension. Here, we investigate room-temperature layer-dependent SCO and insulator-metal transition in vdW magnet,FePS3, under high pressure using micro-Raman scattering.Experimentally obtained spectra, in agreement with the computed Raman modes, indicates evidence of IMT of FePS3 started off with a spin-state transition from a high (S=2) to low spin state (S=0) with a thickness dependent critical pressure (P_c) which reduces to 1.45 GPa in 3-layer flakes compared to 10.8 GPa for the bulk counterpart. Additionally, a broad Raman mode (P*) emerges between 310 cm^{-1} and 370 cm^{-1} at elevated pressure for three different thicknesses of FePS3 flakes (3-100 layers), also corroborated with computational results which suggests the pressure dependent decrease of metal-ligand bond distance(Fe-S) with lowering of magnetic moment in FePS3. Phenomenologically, our results in few-layer flakes with strong structural anisotropy which enhances the in-plane strain with applied pressure can be understood by adopting Hubbard model and considering the spectral-range (bandwidth W) as a function of layer numbers and pressure with a power-law scaling. Reduction of the critical pressure for phase transition in few-layer vdW magnets to 1-2 GPa marks the possibility of using nano-enclosure fit for use in device electronics where the pressure is induced due to interfacial adhesion, like in vdW heterostructure or molecules trapped between layers,and thereby,avoiding the conventional use of diamond anvil cell

How has the OSD affected our state hospitals?

The long-awaited occupation-specific dispensation (OSD) process for state-employed doctors has now been concluded. The final offer, signed and accepted in the bargaining chamber despite being rejected by 92% of doctors in a SAMA survey, has not received much attention or fanfare. At the conclusion of this process, which has been drawn out over several years, many points have emerged that are extremely worrying for the future of health care in this country

Multi-ancestry study of blood lipid levels identifies four loci interacting with physical activity

The present work was largely supported by a grant from the US National Heart, Lung, and Blood Institute (NHLBI) of the National Institutes of Health (R01HL118305). The full list of acknowledgments appears in the Supplementary Notes 3 and 4.Peer reviewedPublisher PD

Reducing the environmental impact of surgery on a global scale: systematic review and co-prioritization with healthcare workers in 132 countries

Abstract Background Healthcare cannot achieve net-zero carbon without addressing operating theatres. The aim of this study was to prioritize feasible interventions to reduce the environmental impact of operating theatres. Methods This study adopted a four-phase Delphi consensus co-prioritization methodology. In phase 1, a systematic review of published interventions and global consultation of perioperative healthcare professionals were used to longlist interventions. In phase 2, iterative thematic analysis consolidated comparable interventions into a shortlist. In phase 3, the shortlist was co-prioritized based on patient and clinician views on acceptability, feasibility, and safety. In phase 4, ranked lists of interventions were presented by their relevance to high-income countries and low–middle-income countries. Results In phase 1, 43 interventions were identified, which had low uptake in practice according to 3042 professionals globally. In phase 2, a shortlist of 15 intervention domains was generated. In phase 3, interventions were deemed acceptable for more than 90 per cent of patients except for reducing general anaesthesia (84 per cent) and re-sterilization of ‘single-use’ consumables (86 per cent). In phase 4, the top three shortlisted interventions for high-income countries were: introducing recycling; reducing use of anaesthetic gases; and appropriate clinical waste processing. In phase 4, the top three shortlisted interventions for low–middle-income countries were: introducing reusable surgical devices; reducing use of consumables; and reducing the use of general anaesthesia. Conclusion This is a step toward environmentally sustainable operating environments with actionable interventions applicable to both high– and low–middle–income countries

Untersuchung von Metall-Wechselwirkungen mit Biomolekülen und π-Akzeptorsystemen : eine genauere Betrachtung von strukturellen Aspekten, elektrochemischen Eigenschaften und spektroskopischen Merkmalen

This thesis contains a study of soft metal interaction with biomolecules or strong π-acceptor ligand systems. Cu(I) complexes with biomolecules have been studied for the investigation of structural aspects to understand the role of metal ions in various biological functions. The proper choice of ligand systems and the necessary modifications are the key to metal-complex synthesis. All biomolecules have been modified and then reacted with organometallic fragments, [Cu(dopf)]+, in aprotic media (dopf = 1,1´-Bis(diorganophosphino)ferrocene. Two types of biomolecules were studied in the course of the doctoral work. Purine nucleobases such as guanine or xanthine and pteridine heterocycles such as lumazine, alloxazine or pterin were modified and their binding to Cu(I) centres was studied. The structural features have been analysed and studied spectroscopically, wherever possible. The labile coordination of biomolecules and their equilibria in solution were also investigated. To enable the isolation of copper complexes, we have utilized various organometallic diphosphines as a scaffolding chelate which not only stabilizes copper(I) but also provides an extra redox active unit. In addition, metal-metal-interactions via σ-donor / π-acceptor bridges have been studied with multinuclear FeCu and Ru complexes. The metal-metal interactions and the light absorption properties have been studied by advanced spectroscopic methods like EPR, spectroelectrochemistry in the Uv-Vis-NIR-IR region and by single crystal X-ray diffraction measurements. Various electrochemical experiments were carried out to investigate the electron transfer processes of the complexes. Electrochemical experiments were also utilized to isolate the radical state of a metal complex.Diese Arbeit enthält eine Studie über die Interaktionen weicher Metalle mit Biomolekülen oder starken π-Akzeptorsystemen. In der Absicht mehr über die Rolle der Metallionen in verschiedenen biologischen Reaktionen zu erhalten, wurden verschiedene Cu(I) Komplexe unterschiedlicher Biomoleküle auf ihre strukturellen Eigenschaften untersucht. Die richtige Wahl bzw. die notwendigen Modifikationen des Ligandensystems stellen den entscheidenden Schritt der Komplexsynthese dar. Alle Biomoleküle wurden modifiziert und mit metallorganischen Fragmenten, [Cu(dopf)], in aprotischen Medien umgesetzt (dopf = 1,1´ Bis(diorganophosphino)ferrocen). Zwei Typen von Biomolekülen wurden im Rahmen dieser Arbeit untersucht. Purin basierte Nukleobasen wie Guanin oder Xanthin und Pteridin basierte Heterozyklen wie Lumazin, Alloxazin oder Pterin wurden modifiziert und ihre Bindungseigenschaften zu Cu(I)-Zentren untersucht. Die strukturellen Eigenschaften wurden analysiert und wann immer möglich Spektroskopisch studiert. Die labile Koordination der Biomoleküle und ihrer Gleichgewichte in Lösung wurden ebenfalls untersucht. Verschiedene metallorganische Diphosphine wurden genutzt, um die Isolierung und Stabilisierung der Kupferkomplexe zu erreichen und eine weitere Redoxaktive Einheit in den Komplex einzubringen. Zusätzlich wurden verschiedene mehrkernige Fe/Cu und Ru Komplexe auf ihre Metall-Metall Interaktion über σ-Donor / π-Akzeptor Brücken untersucht. Die Metall-Metall Interaktionen und die Absorptions Eigenschaften wurden mittels spektroskopischer Methoden wie ESR, Spektroelektrochemie der UV-Vis-NIR-IR Regionen und Einkristall Röntgenstrukturanalyse analysiert. Verschiedene Elektrochemische Experimente wurden durchgeführt um den Elektronentransfer der Komplexe näher zu untersuchen und radikalische Stufen zu isolieren

Designing C₆N₆/C₂N van der Waals heterostructures for photogenerated charge carrier separation

A new two-dimensional C6N6/C2N van der Waals heterostructure is proposed to realize photocatalytic water splitting. The work function difference promotes charge transfer from the C2N to C6N6 layer.</p

Tuning intermediate adsorption in structurally ordered substituted PdCu₃ intermetallic nanoparticles for enhanced ethanol oxidation reaction

Structurally ordered Ni substituted PdCu3 nanoparticles were found to remarkably enhance the ethanol oxidation efficiency due to optimal adsorption of intermediates in close proximity.</p