Multimetallic Oxynitrides Nanoparticles for a New Generation of Photocatalysts

A versatile synthetic strategy for the preparation of multimetallic oxynitrides has been designed and here exemplarily discussed considering the preparation of nanoscaled zinc\u2013gallium oxynitrides and zinc\u2013gallium\u2013indium oxynitrides, two important photocatalysts of new generation, which proved to be active in key energy related processes from pollutant decomposition to overall water splitting. The synthesis presented here allows the preparation of small nanoparticles (less than 20 nm in average diameter), well-defined in size and shape, yet highly crystalline and with the highest surface area reported so far (up to 80 m2 g 121). X-ray diffraction studies show that the final material is not a mixture of single oxides but a distinctive compound. The photocatalytic properties of the oxynitrides have been tested towards the decomposition of an organic dye (as a model reaction for the decomposition of air pollutants), showing better photocatalytic performances than the corresponding pure phases (reaction constant 0.22 h 121), whereas almost no reaction was observed in absence of catalyst or in the dark. The photocatalysts have been also tested for H2 evolution (semi-reaction of the water splitting process) with results comparable to the best literature values but leaving room for further improvement

The effect of silica nanoparticles on the morphology, mechanical properties and thermal degradation kinetics of polycarbonate

Polycarbonate/silica nanocomposites with different silica quantities were prepared by a melt compounding method. The effect of silica amount, in the range 1\u20135 wt.%, on the morphology, mechanical properties and thermal degradation kinetics of polycarbonate (PC) was investigated. Clusters of silica nanoparticles were well dispersed in the polycarbonate whose structure remained amorphous. NMR results showed intermolecular interactions involving the carbonyl groups of different polymeric chains which did not affect the intramolecular rotational motions. The presence of the lowest silica content showed a decrease in the storage and loss moduli below the glass transition temperature, probably due to a plasticization effect. However, an increase in the amount of silica increased the moduli. The presence of silica in PC slightly increased the thermal stability, except for the highest silica content which showed a decrease. The activation energies of thermal degradation for the nanocomposites depended on the amount of silica and on the degree of conversion

Investigating allosteric effects on the functional dynamics of [small beta]2-adrenergic ternary complexes with enhanced-sampling simulations

Signalling by G-protein coupled receptors usually occurs via ternary complexes formed under cooperative binding between the receptor, a ligand and an intracellular binding partner (a G-protein or [small beta]-arrestin). While a global rational for allosteric effects in ternary complexes would be of great help in designing ligands with specific effects, the paucity of structural data for ternary complexes with [small beta]-arrestin, together with the intrinsic difficulty of characterizing the dynamics involved in the allosteric coupling, have hindered the efforts to devise such a model. Here we have used enhanced-sampling atomistic molecular-dynamics simulations to investigate the dynamics and complex formation mechanisms of both [small beta]-arrestin- and Gs-complexes with the [small beta]2-adrenergic receptor (ADRB2) in its apo-form and in the presence of four small ligands that exert different allosteric effects. Our results suggest that the structure and dynamics of arrestin-ADRB2 complexes depend strongly on the nature of the small ligands. The complexes exhibit a variety of different coupling orientations in terms of the depth of the finger loop in the receptor and activation states of ADRB2. The simulations also allow us to characterize the cooperativity between the ligand and intracellular binding partner (IBP). Based on the complete and consistent results, we propose an experimentally testable extended ternary complex model, where direction of the cooperative effect between ligand and IBP (positive or negative) and its magnitude are predicted to be a characteristic of the ligand signaling bias. This paves the avenue to the rational design of ligands with specific functional effects

A Three-Site Mechanism for Agonist/Antagonist Selective Binding to Vasopressin Receptors

Molecular-dynamics simulations with metadynamics enhanced sampling reveal three distinct binding sites for arginine vasopressin (AVP) within its V2 -receptor (V2 R). Two of these, the vestibule and intermediate sites, block (antagonize) the receptor, and the third is the orthosteric activation (agonist) site. The contacts found for the orthosteric site satisfy all the requirements deduced from mutagenesis experiments. Metadynamics simulations for V2 R and its V1a R-analog give an excellent correlation with experimental binding free energies by assuming that the most stable binding site in the simulations corresponds to the experimental binding free energy in each case. The resulting three-site mechanism separates agonists from antagonists and explains subtype selectivity

An Efficient Metadynamics-Based Protocol To Model the Binding Affinity and the Transition State Ensemble of G-Protein-Coupled Receptor Ligands

A generally applicable metadynamics scheme for predicting the free energy profile of ligand binding to G-protein-coupled receptors (GPCRs) is described. A common and effective collective variable (CV) has been defined using the ideally placed and highly conserved Trp6.48 as a reference point for ligand–GPCR distance measurement and the common orientation of GPCRs in the cell membrane. Using this single CV together with well-tempered multiple-walker metadynamics with a funnel-like boundary allows an efficient exploration of the entire ligand binding path from the extracellular medium to the orthosteric binding site, including vestibule and intermediate sites. The protocol can be used with X-ray structures or high-quality homology models (based on a high-quality template and after thorough refinement) for the receptor and is universally applicable to agonists, antagonists, and partial and reverse agonists. The root-mean-square error (RMSE) in predicted binding free energies for 12 diverse ligands in five receptors (a total of 23 data points) is surprisingly small (less than 1 kcal mol–1). The RMSEs for simulations that use receptor X-ray structures and homology models are very similar

Automatic Voter Registration and Voter Turnout in Nevada Elections

For the first time in Nevada’s history, voters who are not registered as Democrats or Republicans (i.e., nonpartisans and minor party registrants) constitute a majority of active registered voters. In particular, the rapid growth in nonpartisan registrants corresponds with Nevada’s adoption of Automatic Voter Registration (AVR) in January 2020, resulting in the addition of more than 320,000 new voters to the electorate. This fact sheet summarizes voter registration and voter turnout statistics reported by the Nevada Secretary of State for elections since 2012

COVID-19 Behind Bars in the Mountain West

Due to overcrowding, inadequate healthcare, systemic neglect, and violence in U.S. carceral (i.e. jails or prisons) and immigration detention centers, these facilities are a hot spot for the spread of COVID-19. In March 2020, the UCLA Law “Covid Behind Bars Data Project” began tracking official agency websites for self-reported data of COVID-19 across prisons, jails, and other detention facilities in the U.S. The number of COVID-19 cases, deaths, and tests performed from 50 state correctional agencies, the District of Columbia’s Department of Corrections, the Federal Bureau of Prisons (BOP), U.S. Immigration and Customs Enforcement (ICE), and several county jail systems are explored in the original report. Due to inconsistencies in data reporting practices across agencies, efforts to collect and standardize COVID-19 data is challenging. This fact sheet explores the available COVID-19 data collected by the UCLA Law “Covid Behind Bars Data Project,” with a focus on agency data reporting and data quality

Surgical Treatment of Spinal Meningiomas in the Elderly (≥75 Years): Which Factors Affect the Neurological Outcome? An International Multicentric Study of 72 Cases

(1) Background: With the increasing life expectancy in the Western world, an increasing number of old patients presents with spinal meningioma. Considering the benign nature of these tumors, the functional outcome remains of great importance, since more people reach old age in general conditions of well-being and satisfactory autonomy. (2) Methods: We conducted an international multicenter retrospective study to investigate demographic, clinical and radiological data in a population of elderly patients (≥75 years of age) undergoing surgery for SM from January 2000 to December 2020 in four European referral centers. The aim was to identify prognostic and predictive factors for a good postoperative functional outcome. (3) Results: 72 patients were included in the study. Complete tumor resection (Simpson I or II) was achieved in 67 (95.7%) cases. Intraoperative complications were reported in 7 (9.9%) patients while postoperative complications were found in 12 (16.7%). An excellent general postoperative status (McCormick I and II) was achieved in 65.3%. Overall, surgical resection had a good impact on patients’ functional outcome (86.1% either showing an improvement or maintaining a good preoperative status). Uni- and multivariate analyses found that both age and preoperative modified McCormick independently correlated with relative outcome (coeff = −0.058, p = 0.0251; coeff = 0.597, p < 0.0001) and with postoperative status (coeff = 0.058, p = 0.02507; coeff = 0.402, p = 0.00027), respectively. (4) Conclusions: Age and preoperative modified McCormick were found to be independent prognostic factors. Nevertheless, advanced age (≥75), per se, did not seem to contraindicate surgery, even in those with severe preoperative neurological deficits. The functional results sustain the need for surgical resection of SM in the elderly

The origin of life: chemical evolution of a metabolic system in a mineral honeycomb?

For the RNA-world hypothesis to be ecologically feasible, selection mechanisms acting on replicator communities need to be invoked and the corresponding scenarios of molecular evolution specified. Complementing our previous models of chemical evolution on mineral surfaces, in which selection was the consequence of the limited mobility of macromolecules attached to the surface, here we offer an alternative realization of prebiotic group-level selection: the physical encapsulation of local replicator communities into the pores of the mineral substrate. Based on cellular automaton simulations we argue that the effect of group selection in a mineral honeycomb could have been efficient enough to keep prebiotic ribozymes of different specificities and replication rates coexistent, and their metabolic cooperation protected from extensive molecular parasitism. We suggest that mutants of the mild parasites persistent in the metabolic system can acquire useful functions such as replicase activity or the production of membrane components, thus opening the way for the evolution of the first autonomous protocells on Earth

Safest Cities in the Mountain West

This fact sheet examines AdvisorSmith’s ranking list of the safest U.S. cities, drawing from the Federal Bureau of Investigation’s (FBI) Uniform Crime Reporting (UCR) dataset released in September 2021. Monthly crime data are presented for violent crimes (e.g. murder, rape, robbery, assault) and property crimes (e.g. burglary, larceny, motor vehicle theft). Data for the Mountain West states of Arizona, Colorado, Nevada, New Mexico, and Utah are included