Tarpjorgensen3245

The spectral signatures associated with different negatively charged exciton complexes (trions) in a WS2 monolayer encapsulated in hBN are analyzed from low temperature and polarization resolved reflectance contrast (RC) and photoluminescence (PL) experiments, with an applied magnetic field. Based on results obtained from the RC experiment, we show that the valley Zeeman effect affects the optical response of both the singlet and the triplet trion species through the evolution of their energy and of their relative intensity, when applying an external magnetic field. Our analysis allows us to estimate a free electron concentration of ∼1.3 × 1011 cm-2. The observed evolutions based on PL experiments on the same sample are different and can hardly be understood within the same simple frame, highlighting the complexity of relaxation processes involved in the PL response.The physical nature of host-guest (HG) interactions occurring between molecular triangles and linear anions was explored using density functional theory (DFT) calculations combined with energy decomposition analyses (EDA), nuclear independent chemical shift (NICS), and non-covalent interaction index (NCI). We demonstrate that (i) in addition to the host being significantly rigid, the strain energies are not negligible, especially for host 2; (ii) halogen anions interact mainly by electrostatic forces (ΔEelst > ΔE > ΔEdisp), meanwhile; (iii) trihalogen anions interact mostly by dispersion forces (ΔEdisp > ΔEelst≈ΔE). The NICS and NCI calculations corroborate the idea that HG interactions are considerably mediated through dispersion terms, and also indicate an antiaromatic character inside the host walls.The Cissus quadrangularis (CQ) stem has interesting nutritional and pharmacological properties to promote the health of the skeletal system. It is a well-recognized plant in the conventional system of medicine in India for treating bone and joint-associated complications. This study focuses on identifying the active constituents from the stem and root extracts of CQ and validating its anti-osteoarthritic activity by the in vivo model. Notable levels of phenolics and flavonoids were found in the ethanol extracts of both CQ stem (CQSE) and root (CQRE), among other solvent fractions. UPLC-MS/MS analysis of these selective extracts resulted in different classes of active compounds from both positive and negative ionization modes. By analyzing their mass spectra and fragmentation pattern, 25 active compounds were identified. The CQSE and CQRE extracts, along with the standard drug (naproxen), were further tested in mono-sodium iodoacetate-induced experimental OA animals. The modulatory effects of the test extracts were assessed by haematology, synovial and cartilage marker profiling, radiology and histopathological analysis. The in vivo findings from the biochemical and physiological studies have led to the conclusion that the CQSE extract is a good choice for the management of OA. The results were substantially better than CQ root extract and naproxen drug-treated groups. Thus, CQS has bioactive constituents, which could facilitate recovery from joint tissue damage, cellular metabolism and associated risk factors attributable to dysfunctions in OA incidence and progression.Reaction of the uranium(iii) metallocenium salt [(CpiPr4)2U][B(C6F5)4] with tert-butyl isocyanide (tBuNC) yielded the dicationic uranium(iv) complex [(CpiPr4)2U(CNtBu)4][B(C6F5)4]2 (1), which displays a linear metallocene geometry. Use of crude mixtures of [(CpiPr4)2U][B(C6F5)4], which contain a soluble source of iodide, led instead to isolation of the monocationic uranium(iv) iodide complex [(CpiPr4)2U(I)(CNtBu)2][B(C6F5)4] (2). Adduct formation with no change in oxidation state was observed upon addition of tBuNC to the neutral uranium(iii) species (CpiPr4)2UI, resulting in isolation of (CpiPr4)2U(I)(CNtBu) (3). X-ray crystallographic and IR spectroscopic studies both showed effects ascribed to the presence of multiple strongly donating isocyanide ligands in 1.Divergence in the PBu3-catalyzed [3+2] annulation of phenacylmalononitriles with allenoates, controlled by the γ-substitution on allenoates, offers a tunable synthesis of multifunctionalized cyclopentene carboxamides and cyclopentenols. An unprecedented formation of cyclopentene carboxamide was observed when allenic esters bearing a substitution at the γ-position were employed, while unsubstituted allenoates produced cyclopentenols. The former reaction likely involves a Michael/aldol/nucleophilic cyclization sequence in a domino manner.The synthesis of benzothioxanthene imide based dimers is reported herein. Subtle chemical modifications were carried out and their impact on the optical and electrochemical properties was investigated for a better structure-property relationship analysis. The icing on the cake was that these new structures were used as light emitting materials for the fabrication and demonstration of the first BTXI-based OLEDs.The new PtVO(SOCR)4 lantern complexes, 1 (R = CH3) and 2 (R = Ph) behave as neutral O-donor ligands to Ln(OR)3 with Ln = Ce, Nd. Four heterotrimetallic complexes with linear LnOVPt units were prepared [Ln(ODtbp)3PtVO(SOCR)4] (Ln = Ce, 3Ce (R = CH3), 4Ce (R = Ph); Nd, 3Nd (R = CH3), 4Nd (R = Ph); ODtbp = 2,6-ditertbutylphenolate). Magnetic characterization confirms slow magnetic relaxation behaviour and suggests antiferromagnetic coupling across Ln-O[double bond, length as m-dash]V in all four complexes, with variations tunable as a function of Ln and R.Okra is a vegetable crop very popular in tropical, subtropical, and warm temperate regions of the world for its edible fruit. Nowadays, this species can be easily found in European local markets, as a basic ingredient in many local and traditional dishes. Considering the extensive and spread use of okra fruits, to achieve deep insight on its chemical composition the analysis of the polar extract by high-performance liquid chromatography coupled to multiple-stage linear ion-trap and orbitrap high-resolution mass spectrometry in negative electrospray ionization mode was carried out. By this approach, 39 metabolites belonging to different polar lipid classes, such as oxylipins, phospholipids, glycolipids, and sphingolipids, were putatively identified for the first time in A. esculentus. Moreover, LC-HRMS/MS analyses guided the isolation and characterization by NMR experiments of 19 specialized metabolites belonging to phenolic acid and flavonoid classes, 8 of them never reported before in A. esculentus. Finally, antioxidant activity and inhibition of α-glucosidase activity were assayed, suggesting a good anti-oxidant anti-hyperglycemic activity for okra fruit.In the early 1990s chiral P-thiother ligands emerged as promising ligands in the field of asymmetric catalysis, with the development of many P-thioether ligand families. However, only a few of them have shown a broad reaction and substrate scope. So, compared with other heterodonor ligands such as the widely studied P-N ligands, their impact in asymmetric catalysis was not realised until recently. This has been mainly attributed to the difficulty of controlling the configuration at the sulfur atom when coordinated to the metal. More recently, it has been found that this problem could be solved by a rigorous choice of the ligand scaffold, a process usually aided by mechanistic studies. This allowed the recent discovery of new P-thioether ligand families with a broader versatility, both in reactions and in substrate/reagent scope. This feature article aims to highlight those new P-thioether ligand libraries and the relationship between the structure and catalytic performance.As a type of biological macromolecule, the conformation of proteins dynamically changes in a solution, which often results in a change in their function. However, traditional biological assays have significant drawbacks in detecting the conformation properties of proteins. Alternatively, nanopores have potential advantages in this area, which can detect protein in high throughput and without labelling. Herein, we investigated the translocation of calmodulins through silicon nitride nanopores using molecular dynamics (MD) simulation. Initially, the calmodulins were fixed in the nanopore. Distinguished blocked ionic currents were obtained between the two forms of calmodulin. Next, in the translocation simulations, a prominent difference in time resolution was easily found between the two states of calmodulin by using the appropriate voltage and comparable size of pore to protein, rp/rg→ 1, 4.5 nm (where rp is the protein radius and rg is the gyration radius). These simulations on the nanoscale are helpful for developing Ca2+-sensitive ion channels and nanodevices.Neutron reflectivity (NR) measurements have been employed to study the interfacial structuring and composition of electroresponsive boundary layers formed by an ionic liquid (IL) lubricant at an electrified gold interface when dispersed in a polar solvent. The results reveal that both the composition and extent of the IL boundary layers intricately depend on the bulk IL concentration and the applied surface potential. At the lowest concentration (5% w/w), a preferential adsorption of the IL cation at the gold electrode is observed, which hinders the ability to electro-induce changes in the boundary layers. In contrast, at higher IL bulk concentrations (10 and 20% w/w), the NR results reveal a significantly larger concentration of the IL ions at the gold interface that exhibit significantly greater electroresponsivity, with clear changes in the layer composition and layer thickness observed for different potentials. In complementary atomic force microscopy (AFM) measurements on an electrified gold surface, such IL boundary layers are demonstrated to provide excellent friction reduction and electroactive friction (known as tribotronics). In agreement with the NR results obtained, clear concentration effects are also observed. Together such results provide valuable molecular insight into the electroactive structuring of ILs in solvent mixtures, as well as provide mechanistic understanding of their tribotronic behaviours.Endothelial dysfunction is associated with cardiovascular diseases and involves a chronic inflammatory process that together with oxidative stress increases the permeability of the vascular endothelium. The aim of this study was to evaluate the role of red and white wine pomace products (rWPPs and wWPPs) in the maintenance of endothelial integrity in hyperglycemia of EA.hy926 endothelial cells. EA.hy926 endothelial cells exposed to hyperglycemia were treated with the in vitro digested fractions of rWPPs and wWPPs. A Real Time Cellular Analysis (RTCA) system was used to evaluate the endothelial monolayer integrity after INF-γ stimulation of pre-treated endothelial cells with the digested fractions. The changes in cell viability, NO, ROS and NOX4 were recorded and actin cytoskeleton and E-cadherin junctions were evaluated by immunofluorescence. All digested fractions prevent the hyperglycemic actions in the cell viability and NO/ROS balance. The inflammatory mediator INF-γ and hyperglycemia caused a decrease in RTCA adhesion of the EA.