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Nanoscale Jan 20245d transition-metal compounds are usually not expected to exhibit distinct magnetic ordering owing to their substantial binding energy associated with 5d electrons. In...
5d transition-metal compounds are usually not expected to exhibit distinct magnetic ordering owing to their substantial binding energy associated with 5d electrons. In this study, we demonstrate that two-dimensional (2D) 5d transition-metal Os trihalide OsX monolayers can exhibit room-temperature ferromagnetism and quantum anomalous Hall effect (QAHE) by utilizing density functional theory and Monte Carlo simulation. Our calculation results of coexisting Raman and infrared activities of lattice vibration reveal the structural stability of 2D OsX (X = Cl, Br, I) and structural instability of 2D OsX (X = F). Furthermore, all 2D OsX trihalides (X = Cl, Br, I) are half-metals, and their ferromagnetism remains stable under ambient temperature, where 2D OsCl and OsBr have an in-plane easy axis while 2D OsI has an out-of-plane easy axis. Notably, when spin-orbit coupling is included, the gate-tunable QAHE could emerge in ferromagnetic 2D OsI, while 2D OsCl and OsBr are topologically trivial. Additionally, the magnon bands of 2D OsX (X = Cl, Br, I) possess two spin-wave branches with dispersion similar to that of the Dirac cone in the electronic structure of graphene, which are attributed to the unique ferromagnetic honeycomb sublattice of osmium atoms.
PubMed: 38131394
DOI: 10.1039/d3nr02985a -
Advanced Healthcare Materials Mar 2024Acute kidney injury (AKI) is a common adverse event in chemotherapy patients. AKI is accompanied by the generation of reactive oxygen species (ROS) and inflammation....
Acute kidney injury (AKI) is a common adverse event in chemotherapy patients. AKI is accompanied by the generation of reactive oxygen species (ROS) and inflammation. Therefore, the management of ROS and inflammation is a potential strategy for AKI mitigation. Herein, polyethylene glycol-coated osmium nanozyme-based antidotes (Os) are developed for imaging-guided photothermal therapy (PTT) in combination with cisplatin (Pt); while, avoiding AKI induced by high-dose Pt. Os nanoantidotes can enhance the efficiency of tumor treatment during combined PTT and chemotherapy and inhibit tumor metastasis by improving the hypoxic and inflammatory tumor microenvironment. Os nanoantidotes preferentially accumulate in the kidney because of their 2-nm size distribution; and then, regulate inflammation by scavenging ROS and generating oxygen to alleviate Pt-induced AKI. Os nanoantidotes can be cleared from the kidneys by urine excretion but can be degraded under hydrogen peroxide stimulation, reducing the bio-retention of these compounds. By integrating PTT with inflammatory regulation, Os nanoantidotes have the potential to reduce the side effects of chemotherapy, offering an alternative route for the clinical management of cancer patients with chemotherapy-induced AKI.
Topics: Humans; Osmium; Reactive Oxygen Species; Acute Kidney Injury; Neoplasms; Inflammation; Antineoplastic Agents; Cell Line, Tumor; Tumor Microenvironment
PubMed: 38097368
DOI: 10.1002/adhm.202302729 -
Chemphyschem : a European Journal of... Mar 2024Osmium carbonyls are well known to form stable 18-electron complexes like Os(CO) , Os (CO) and Os (CO) having both bridging and terminal carbonyls. For osmium...
Osmium carbonyls are well known to form stable 18-electron complexes like Os(CO) , Os (CO) and Os (CO) having both bridging and terminal carbonyls. For osmium tetra-carbonyl, Os(CO) solid-state packing significantly alters the ground-state structure. The gas-phase stable see-saw geometry converts to a square-planar structure in solid state. Highly efficient intermolecular stacking between Os(CO) units assists this transformation. Each Os(CO) molecule is stacked in a staggered orientation with respect to each other. Pressure induces a [Xe]4f 5d 6s (S=2)→[Xe]4f 5d (S=0) electronic transition in osmium stabilize a square planar osmium tetra-carbonyl. Under the influence of isotropic pressure, the molecules not only come closer to each other but their relative orientations also get significantly altered. Calculations show that at P=1 GPa and above, the eclipsed orientation for the intermolecular stacking gets preferred over the staggered form. The staggered→eclipsed intermolecular stacking orientation under pressure is shown to be controlled by London dispersion interactions.
PubMed: 38087878
DOI: 10.1002/cphc.202300720 -
Scientific Reports Dec 2023The Turonian age (~ 90-94 Ma) was the hottest geological interval in the Cretaceous and also marked by the K3 event, a pronounced enrichment of He in pelagic...
The Turonian age (~ 90-94 Ma) was the hottest geological interval in the Cretaceous and also marked by the K3 event, a pronounced enrichment of He in pelagic sediments (i.e., massive input of extraterrestrial materials). Here, we present Os isotopic (Os/Os) and platinum group element (PGE) data from Turonian sedimentary records. After a sharp unradiogenic shift during the end-Cenomanian oceanic anoxic event 2, the Os/Os ratios declined continuously throughout the Turonian, which could be ascribed to the formations of several large igneous provinces (LIPs). Because the interval with the most unradiogenic Os/Os ratios (i.e., enhanced LIP volcanism) does not correspond to the warmest interval during the mid-Cretaceous, additional sources of CO, such as subduction zone volcanism or the kimberlite formation, may explain the Cretaceous Thermal Maximum. As Os isotope ratios do not show any sharp unradiogenic shifts and PGE concentrations do not exhibit a pronounced enrichment, an influx of fine-grained cosmic dust to the Earth's surface, possibly from the long-period comet showers, can be inferred at the time of the He enrichment during the mid-Turonian K3 event. Our findings highlight the different behaviors of He and PGE information in the sedimentary rocks during the input of fined-grained extraterrestrial materials.
PubMed: 38086887
DOI: 10.1038/s41598-023-49252-5 -
Data in Brief Dec 2023This paper presents a dataset offering profound insights into the formation and physical properties of two-dimensional (2D) noble metals under various configurations,...
This paper presents a dataset offering profound insights into the formation and physical properties of two-dimensional (2D) noble metals under various configurations, with a primary focus on their role as catalysts for the hydrogen evolution reaction (HER). These data are of significant value to catalysis researchers, materials scientists, and computational chemists, providing them with a detailed understanding of 2D noble metals' behavior as catalysts and enabling advancements in their respective studies. The dataset, thoughtfully structured and meticulously documented, comprises five primary sections, each housing distinct content and analyses. It offers a comprehensive view of the substrate-mediated stabilization and physical properties of 2D noble metals, including silver (Ag), gold (Au), iridium (Ir), osmium (Os), palladium (Pd), platinum (Pt), rhodium (Rh), and ruthenium (Ru). The substrates utilized include bare Si-face 4H-SiC, buffer layer (BuL), and monolayer epitaxial graphene (MEG). The data collection process involves the use of the SIESTA code for density functional theory (DFT) calculations. The vdW-BH functional is consistently applied in conjunction with a double-ζ polarized (DZP) basis set, known for its reliability in capturing nuanced interactions with noble metals. Parameters such as an energy shift of 200 meV and a force tolerance of 0.02 eV/Å are meticulously configured for accurate results. In-depth structural information, including optimized structures in top and side views and Cartesian coordinates for various substrate-metal configurations, is a central component of the dataset. These structural details are pivotal for comprehending the physical properties of 2D noble metals. Furthermore, the dataset encompasses results from charge density difference (CDD) analyses, including cube files, planar-averaged CDD curves, and 3D CDD maps. These analyses provide essential data for understanding the electronic properties of these materials. The dataset also includes outcomes from charge population analyses utilizing Hirshfeld and Voronoi schemes. These analyses offer insights into structural parameters, Hirshfeld charge magnitudes on 2D metal layers, and various energy-related metrics, further enhancing the dataset's richness. In addition to structural data, the dataset presents atomic structures in top and side views of free-standing and substrate-supported 2D noble metals after hydrogen adsorption, along with corresponding Cartesian coordinates. Gibbs free energy (Δ) data for hydrogen adsorption on both free-standing and substrate-supported 2D noble metals contribute to the dataset's depth. This meticulously curated dataset not only serves as a valuable resource for researchers exploring the properties and behaviors of 2D noble metals but also holds significant reuse potential. Researchers can employ this dataset to validate their computational methods and models in catalysis research, enhancing the quality and reliability of their simulations. Furthermore, it serves as a possible educational tool, fostering hands-on learning for students and emerging researchers in the field of computational materials science and catalysis, thereby promoting methodological consistency within the scientific community.
PubMed: 38053595
DOI: 10.1016/j.dib.2023.109801 -
Inorganic Chemistry Dec 2023Herein, we disclose a unique method of oxidation of a 1,4-naphthoquinone ring in air. We report that (1,4-naphthoquinone)-NH-N=C(OH)Ph (HL) coordinated to octahedral...
Herein, we disclose a unique method of oxidation of a 1,4-naphthoquinone ring in air. We report that (1,4-naphthoquinone)-NH-N=C(OH)Ph (HL) coordinated to octahedral ruthenium(II) and osmium(II) ions activates an O molecule spontaneously. Hydrogen atom transfer (HAT) from the -NH- function of HL to O and subsequent (2e + 2H) oxidation forming (1,3,4-trioxonaphthalen)=N-N=C(OH)Ph (HL) have been established. The HL → HL transformation occurs via (3-hydroperoxy-1,4-naphthoquinone)=N-N=C(O)Ph (HL) as an intermediate. The primary step is HAT generating HL and hydroperoxide (OOH) radicals. HL is delocalized over the aromatic ring and incites coupling reactions via ortho carbon and produces coordinated HL. In solution, the homolytic cleavage of the peroxo bond leads to aromatic ring oxidation, affording L. Ruthenium(II) and osmium(II) complexes of the types [M(HL)(PPh)X], [M(HL)(PPh)X], and -[M(L)(PPh)X] were successfully isolated in good yields. Notably, the cyclic voltammograms of all of the complexes exhibit reversible anodic waves due to M/M redox couples. The rate constants of the [M(HL)(PPh)X] → [M(HL)(PPh)X] conversions determined by time-driven UV-vis spectroscopy in dry CHCl, wet CHCl, and DO wet CHCl in air at 298 K follow the order > > . It is established that the rate constants are dependent on the O content of the solution but not on the concentration of the complex.
PubMed: 38047920
DOI: 10.1021/acs.inorgchem.3c03038 -
Carbohydrate Research Dec 2023Bacterial natural products containing heptosides such as septacidin represent interesting scaffolds for the development of drugs to combat antimicrobial resistance....
Bacterial natural products containing heptosides such as septacidin represent interesting scaffolds for the development of drugs to combat antimicrobial resistance. However, very few synthetic strategies have been reported to grant access to these derivatives. Here, we have devised a synthetic pathway to l-glycero-l-glucoheptoside, a key building block en route to septacidin, directly from l-glucose. Importantly, we show that carbon homologation at C6, encompassing oxidation of the C6-OH followed by methylenation, is significantly influenced by the nature of the C4-moiety. In order to observe the effect of various patterns, namely azide (N), p-methoxybenzyloxy (OPMB), and benzyloxy (OBn), a thorough analysis was conducted on the corresponding l-glucosides. The results unveiled a distinct trend where the efficiency of methylenation followed the trend OBn > OPMB > N. Finally, the C6-alkene was dihydroxylated in the presence of osmium tetroxide to yield the expected l/d-glycero-l-glucoheptosides. The lead building block, which features a C-4 azide, was delivered as a phenyl thioglycoside. Added to the suitable masking of the 6,7-diol, this combination enables further functionalization to achieve versatile compounds of biological interest. The study insights into the interplay between substitution at C-4 and carbon homologation at C-6 provide valuable guidance for future endeavors in the synthesis of these carbohydrate molecules.
Topics: Glucose; Azides; Heptoses; Carbon
PubMed: 38016254
DOI: 10.1016/j.carres.2023.108985 -
Chemistry, An Asian Journal Jan 2024In recent years, the field of organometallic chemistry has made a great progress and diverse types of metallaaromatics have successively been reported. In those studies,... (Review)
Review
In recent years, the field of organometallic chemistry has made a great progress and diverse types of metallaaromatics have successively been reported. In those studies, incorporation of ligated osmium centers into metallaaromatic systems played a prominent role. The reviewed literature documents that certain metallaaromatics with unconventional photophysical properties, redox and electronic transport properties and magnetism, have potential to be widely used in diverse practical applications, with selected examples of amino acid and fluoride anion identification, photothermal effects, functional materials, photodynamic therapy (PDT) in biomedicine, single-molecule junction conductors, and electron-transport layer materials (ETLs) in solar cells.
PubMed: 37997007
DOI: 10.1002/asia.202300860 -
Clinical Toxicology (Philadelphia, Pa.) Nov 2023Osmium tetroxide is a strong oxidizing agent. After dermal exposure to osmium tetroxide, skin discoloration and red papules can occur. We describe a patient with skin...
INTRODUCTION
Osmium tetroxide is a strong oxidizing agent. After dermal exposure to osmium tetroxide, skin discoloration and red papules can occur. We describe a patient with skin discoloration due to osmium tetroxide.
CASE SUMMARY
A 25-year-old postgraduate student unintentionally exposed his hand to osmium tetroxide while working in a laboratory setting. After immediate washing, he sought medical care due to left middle finger discoloration. He reported no discomfort in the affected area. Thorough water rinsing was continued, and corticosteroid ointment was applied.
IMAGES
Our patient developed dark brown pigmentation on the ventral side of the left middle finger. The pigmentation disappeared one week later.
CONCLUSION
Osmium tetroxide may induce dark brown skin discoloration.
Topics: Adult; Humans; Male; Osmium Tetroxide; Skin Diseases
PubMed: 37987740
DOI: 10.1080/15563650.2023.2281253 -
Chemistry (Weinheim An Der Bergstrasse,... Feb 2024Macrocyclic and medium-sized ring ketones, lactones and lactams can all be made from common acryloyl imide starting materials through divergent, one-pot cascade...
Macrocyclic and medium-sized ring ketones, lactones and lactams can all be made from common acryloyl imide starting materials through divergent, one-pot cascade ring-expansion reactions. Following either conjugate addition with an amine or nitromethane, or osmium(VIII)-catalysed dihydoxylation, rearrangement through a four-atom ring expansion takes place spontaneously to form the ring expanded products. A second ring expansion can also be performed following a second iteration of imide formation and alkene functionalisation/ring expansion. In the dihydroxylation series, three- or four-atom ring expansion can be performed selectively, depending on whether the reaction is under kinetic or thermodynamic control.
PubMed: 37987097
DOI: 10.1002/chem.202303270