From electronic structure to catalytic activity: A single descriptor for adsorption and reactivity on transition-metal carbides

Adsorption and catalytic properties of the polar (111) surface of transition-metal carbides (TMC's) are investigated by density-functional theory. Atomic and molecular adsorption are rationalized with the concerted-coupling model, in which two types of TMC surface resonances (SR's) play key roles. The transition-metal derived SR is found to be a single measurable descriptor for the adsorption processes, implying that the Br{\o}nsted-Evans-Polanyi relation and scaling relations apply. This gives a picture with implications for ligand and vacancy effects and which has a potential for a broad screening procedure for heterogeneous catalysts.Comment: 5 pages, 3 figure

Steam reforming on transition-metal carbides from density-functional theory

A screening study of the steam reforming reaction (CH_4 + H_2O -> CO + 3H_2) on early transition-metal carbides (TMC's) is performed by means of density-functional theory calculations. The set of considered surfaces includes the alpha-Mo_2C(100) surfaces, the low-index (111) and (100) surfaces of TiC, VC, and delta-MoC, and the oxygenated alpha-Mo_2C(100) and TMC(111) surfaces. It is found that carbides provide a wide spectrum of reactivities towards the steam reforming reaction, from too reactive via suitable to too inert. The reactivity is discussed in terms of the electronic structure of the clean surfaces. Two surfaces, the delta-MoC(100) and the oxygen passivated alpha-Mo_2C(100) surfaces, are identified as promising steam reforming catalysts. These findings suggest that carbides provide a playground for reactivity tuning, comparable to the one for pure metals.Comment: 6 pages, 4 figure

Surface Rearrangement and Evaporation Kinetics of Supported Gold Nanoparticle Catalysts

Heterogeneous catalysts consisting of supported metallic nanoparticles typically derive exceptional catalytic activity from their large proportion of under-coordinated surface sites which promote adsorption of reactant molecules. Simultaneously, these high energy surface configurations are unstable, leading to nanoparticle growth or degradation, and eventually a loss of catalytic activity. Surface morphology of catalytic nanoparticles is paramount to catalytic activity, selectivity, as well as degradation rates, however, it is well-known that harsh reaction conditions can cause the surface structure to change. Still, limited research has focused on understanding the link between nanoparticle surface facets and degradation rates or mechanisms. Here, we study a model Au supported catalyst system over a range of temperatures using a combination of \textit{in situ} Transmission Electron Microscopy, kinetic Monte Carlo simulations, and density functional theory calculations to establish an atomistic picture of how variations in surface structures and atomic coordination environments lead to shifting evolution mechanisms as a function of temperature. By combining experimental results, which yield direct observation of dynamic shape changes and particle evaporation rates, with computational techniques, which enable understanding the fundamental thermodynamics and kinetics of nanoparticle evolution, we illustrate a two-step evolution mechanism in which mobile adatoms form through desorption from low-coordination facets and subsequently evaporate off the particle surface. By understanding the role of temperature in the competition between surface diffusion and evaporation, we are able to show how individual atomic movements lead to particle-scale morphological changes, and rationalize why evaporation rates vary between particles in a system of nearly identical nanoparticles

Ant colonies prefer infected over uninfected nest sites

During colony relocation, the selection of a new nest involves exploration and assessment of potential sites followed by colony movement on the basis of a collective decision making process. Hygiene and pathogen load of the potential nest sites are factors worker scouts might evaluate, given the high risk of epidemics in group-living animals. Choosing nest sites free of pathogens is hypothesized to be highly efficient in invasive ants as each of their introduced populations is often an open network of nests exchanging individuals (unicolonial) with frequent relocation into new nest sites and low genetic diversity, likely making these species particularly vulnerable to parasites and diseases. We investigated the nest site preference of the invasive pharaoh ant, Monomorium pharaonis, through binary choice tests between three nest types: nests containing dead nestmates overgrown with sporulating mycelium of the entomopathogenic fungus Metarhizium brunneum (infected nests), nests containing nestmates killed by freezing (uninfected nests), and empty nests. In contrast to the expectation pharaoh ant colonies preferentially (84%) moved into the infected nest when presented with the choice of an infected and an uninfected nest. The ants had an intermediate preference for empty nests. Pharaoh ants display an overall preference for infected nests during colony relocation. While we cannot rule out that the ants are actually manipulated by the pathogen, we propose that this preference might be an adaptive strategy by the host to "immunize" the colony against future exposure to the same pathogenic fungus

Emerging drugs for the treatment of vitiligo

Introduction: Vitiligo is a relatively common autoimmune depigmenting disorder of the skin. There has been a great advance in understanding the pathological basis, which has led to the development and utilization of various new molecules in treating vitiligo. This review aims at a comprehensively describing the treatments available and the emerging treatment aspects and the scope for future developments. Areas covered: This study comprehensively summarizes the current concepts in the pathogenesis of vitiligo with special focus on the cytokine and signaling pathways, which are the targets for newer drugs. JAK kinase signaling pathways and the cytokines involved are the focus of vitiligo treatment in current research, followed by antioxidant mechanisms and repigmenting mechanisms. Topical immunosuppressants may be an alternative to steroids in localized vitiligo. Newer repigmenting agents like basic fibroblast growth factors, afamelanotide have been included and a special emphasis is laid on the upcoming targeted immunotherapy. Expert opinion: The treatment of vitiligo needs to be multimodal with emphasis on targeting different limbs of the pathogenesis. Topical and oral JAK inhibitors are the most promising new class of drugs currently available for treating vitiligo and acts best in conjunction with NB-UVB

Patterns of rapid weight loss in elite sambo athletes

Background: Rapid weight loss (RWL) is commonly practiced in combat sports. Both magnitude and methods used to induce RWL are largely similar among combat sports, but currently, there is no data on RWL methodology used by sambo athletes. Therefore, the aim of this study was to determine RWL procedures sambo athletes apply to lose weight rapidly. Methods: The sample consisted of 199 participants, of which 132 males and 67 females who participated in the World Sambo Championship 2020 held in Novi Sad, Serbia. Each participant received RWL questionnaire that was available in multiple languages, and every participant was instructed how to fill it out. Results: Almost 87% of sambo participants declared to have intentionally cut their weight prior to the competition, whereby 5.27 kg (SD: ±7.57) was lost. Gradual dieting, sauna use and skipping meals were the most dominant methods used to reduce weight prior to competition while more extreme methods of RWL such as the use of laxatives, diuretics, diet pills and vomiting were also implemented but by much smaller fragment of the participants involved. Conclusions: Findings from our study largely match with previously conducted RWL studies in terms of prevalence, magnitude and methods used by combat sport athletes, especially in judo and wrestling. Knowing the hazardous consequences of RWL, alternative methods of sustainable weight loss should be considered

Ant Colonies Prefer Infected over Uninfected Nest Sites

During colony relocation, the selection of a new nest involves exploration and assessment of potential sites followed by colony movement on the basis of a collective decision making process. Hygiene and pathogen load of the potential nest sites are factors worker scouts might evaluate, given the high risk of epidemics in group-living animals. Choosing nest sites free of pathogens is hypothesized to be highly efficient in invasive ants as each of their introduced populations is often an open network of nests exchanging individuals (unicolonial) with frequent relocation into new nest sites and low genetic diversity, likely making these species particularly vulnerable to parasites and diseases. We investigated the nest site preference of the invasive pharaoh ant, Monomorium pharaonis, through binary choice tests between three nest types: nests containing dead nestmates overgrown with sporulating mycelium of the entomopathogenic fungus Metarhizium brunneum (infected nests), nests containing nestmates killed by freezing (uninfected nests), and empty nests. In contrast to the expectation pharaoh ant colonies preferentially (84%) moved into the infected nest when presented with the choice of an infected and an uninfected nest. The ants had an intermediate preference for empty nests. Pharaoh ants display an overall preference for infected nests during colony relocation. While we cannot rule out that the ants are actually manipulated by the pathogen, we propose that this preference might be an adaptive strategy by the host to “immunize” the colony against future exposure to the same pathogenic fungus

Cardiovascular drug use and differences in the incidence of cardiovascular mortality in elderly Seriban men

Objective:To assess whether the difference in risk of cardiovascular mortality between urban and rural areas of Serbia could be explained by differences in the use of cardiovascular medication. Methods: The Serbian cohorts of the Seven Countries Study, Velika Krsna (VK), Zrenjanin (ZR) and Belgrade (BG), were enrolled in 1962-1964 and were followed up for 25 years. The survivors of these cohorts were re-examined in 1987, 1988 and 1989, respectively. This second examination of elderly men aged 65 to 84 years included a questionnaire about current use of cardiovascular medication, risk factors and diseases and a physical examination. All subjects were followed until death or the predefined censor date (10 years after baseline). The Cox proportional hazards model was used to calculate the risk of cardiovascular mortality in the rural cohorts compared to the urban cohort and to adjust for confounding. Main outcome measure: Cardiovascular death. Results: A total of 227 men from VK, 184 men from ZR and 287 men from BG were followed for a mean duration of 7.4 years and was complete for all subjects. After exclusion of 13 subjects with missing medication data, the incidences of cardiovascular mortality in VK, ZR, and BG were 60, 74, and 26 per 1000 person-years, respectively. The prevalence of cardiovascular medication use was 38% in VK, 52% in ZR, and 59% in BG. The greatest difference in use of specific medication was observed for betablockers (0% in VK and ZR, 13% in BG). After adjustment for cardiovascular risk factors, diseases and age, the relative risks (RRs) of cardiovascular mortality were 2.12 [95% CI: 1.44¿3.12], and 2.27 [95% CI: 1.56¿3.30] in VK, and ZR compared to BG. Additional adjustment for the use of cardiovascular medication increased these RRs to 2.40 [95% CI: 1.61¿3.60] and 2.55 [95% CI: 1.72¿3.78], respectively. Conclusion:The variation in cardiovascular medication use could not explain the excess risk of mortality in the rural Serbian cohorts compared to urban Belgrade

Evaluation of the glycemic effect of methotrexate in psoriatic arthritis patients with metabolic syndrome. a pilot study

Methotrexate (MTX) is a systemic immunosuppressant drug used for the treatment of psoriasis and psoriatic arthritis. Previous studies demonstrated a potential association between psoriasis and diabetes mellitus, obesity, atherosclerosis, hypertension, eventuating into metabolic syndrome. This study aimed at exploring the glycemic effects of MTX in psoriatic arthritis (PsA) patients. In this prospective cross-sectional study, 27 patients with PsA were evaluated. The status of PsA and presence of accompanying metabolic syndrome was determined by standard criteria and indices. Blood indicators including HbA1c, erythrocyte sedimentation rate, fasting blood sugar, total cholesterol, high-density lipoprotein, triglycerides, and C-reactive protein were examined before and 12 weeks after MTX therapy. There were no significant changes between HbA1c levels before and after MTX therapy in both genders (men: P=0.131, women: P=0.803). In addition, HbA1c levels in PsA patients with metabolic syndrome were not different before and after treatment (P=0.250). Finally, HbA1c levels did not change in PsA patients without metabolic syndrome before and after therapy (P=0.506). MTX in PsA patients does not appear to have hyperglycaemic effects in the short-term and can be safely used in patients with metabolic syndrome and diabete