On the Surface Restructuring of Highly Dilute Alloys and its Effects on Catalytic Performance

Recent studies have shown that highly dilute alloys of platinum group metals (PGMs: Pt, Rh, Ir and Pd) with coinage metals (Cu, Au, and Ag) serve as highly selective and coke–resistant catalysts in a number of important chemical reactions. These materials are composed of trace amounts of a PGM or Ni, whose atoms are embedded in a coinage metal surface, and their catalytic behaviour is governed by the size and shape of the surface clusters of PGM atoms. Therefore, establishing a means of control over the topological architecture of highly dilute alloy surfaces is crucial to achieving catalytic performance tailored to a specific application. This Thesis employs density functional theory, kinetic Monte Carlo and microkinetic modelling in order to investigate ways of manipulating the surface architecture of a number of dilute alloy surfaces towards optimal performance for key catalytic reactions. The latter include the direct dissociations of NO, CO2 and N2, and the reverse events, which are important in, among others, emission control technologies. Also examined is the potential of a Ni/Cu dilute alloy for the NO + CO chemistry, and it is demonstrated that the selectivity toward the desired products can be manipulated by tuning the size of the Ni clusters in the ensemble. The results can guide future theoretical, surface science and catalysis studies on highly dilute alloys, towards the development of superior catalysts that can efficiently accelerate chemistries of industrial significance

Heat transfer across a fractal surface

The effects of surface irregularities and imperfections on the thermal resistance at a solid-liquid interface have been investigated using molecular dynamics. The molecular model comprises liquid argon confined between silver walls. The surface roughness was designed using fractal theory, introducing stochastic patterns of multiple scales that resemble realistic surface geometries. In agreement with most previous studies, we find that increasing the strength of the solid-liquid interactions monotonically reduces the thermal resistance across smooth interfaces. Yet, the behavior of the thermal resistance across rough surfaces is more complex. Following the initially anticipated decrease, the thermal resistance starts to increase once the strength of solid-liquid interaction increases past a threshold. We attribute the above behavior to two competing phenomena, namely, the area of the solid-liquid interface and the introduction of vibrational anharmonicities and localization of phonons resulting from the surface roughness. Finally, we demonstrate that, for the same fractal dimension and depth of surface roughness, different surfaces practically have the same thermal resistance, solid-liquid radial distribution function, and liquid density profiles. We conclude that the above fractal parameters are useful in deriving reduced models for properties related to the surface geometry

Exercise and redox status responses following alpha-lipoic acid supplementation in G6PD deficient individuals

G6PD deficiency renders cells more susceptible to oxidative insults, while antioxidant dietary supplementation could restore redox balance and ameliorate exercise-induced oxidative stress. To examine the effects of alpha-lipoic acid (ALA) supplementation on redox status indices in G6PD deficient individuals, eight male adults with G6PD deficiency (D) participated in this randomized double-blind placebo-controlled crossover trial. Participants were randomly assigned to receive ALA (600 mg/day) or placebo for 4 weeks separated by a 4-week washout period. Before and at the end of each treatment period, participants exercised following an exhaustive treadmill exercise protocol. Blood samples were obtained before (at rest), immediately after and 1h after exercise for later analysis of total antioxidant capacity (TAC), uric acid, bilirubin, thiobarbituric acid reactive substances (TBARS) and protein carbonyls (PC). ALA resulted in significantly increased resting TAC and bilirubin concentrations. Moreover, TAC increased immediately and 1h after exercise following both treatment periods, whereas bilirubin increased immediately after and 1h after exercise following only ALA. No significant change in uric acid, TBARS or PC was observed at any time point. ALA supplementation for 4 weeks may enhance antioxidant status in G6PD individuals; however, it does not affect redox responses to acute exercise until exhaustion or exercise performance

An outbreak of hemodialysis catheter-related bacteremia with sepsis caused by Streptococcus agalactiae in a hemodialysis unit

AbstractBackgroundRates of invasive group B Streptococcus (GBS; Streptococcus agalactiae) disease in adults are on the rise. Invasive GBS disease can be community- or healthcare-associated. We report an outbreak of GBS catheter-related bacteremia in a hemodialysis (HD) unit.Materials and methodsTwo patients undergoing HD at the same outpatient HD unit were admitted on the same day (within a few hours of each other) with catheter-related GBS bacteremia. A retrospective study was undertaken at the HD unit to address risk factors for febrile illness on the last HD session day. A detailed questionnaire was completed by all HD patients treated on the same day as the two GBS patients and by all members of the nursing and medical staff. Medical and nursing records of the HD unit were reviewed, as well as infection control and catheter care practices. Patients and staff members submitted swabs for culture.ResultsNo rectal or vaginal culture of any HD patient or staff member was positive for GBS. The development of recent febrile disease was significantly associated with the presence of a hemodialysis catheter (p=0.028) and care for more than 30min by a specific nurse during the last two HD sessions (p=0.007).ConclusionsWe speculate that the GBS strain was transmitted from one patient to the other through the hands of medical personnel. No such outbreak has ever been reported in HD patients. The importance of strict infection control practices in HD units and the avoidance of catheters for long-term HD should be emphasized

Improving the ORR Performance by Enhancing the Pt Oxidation Resistance

Proton exchange membrane fuel cells require oxygen reduction catalysts with high activity and stability. Pt based alloy materials are most widely applied ORR catalyst due to its high intrinsic activity, but usually suffer from rapid deactivation as a result of particle agglomeration, detachment, Ostwald ripening and/or Pt dissolution. Here we investigate the degradation of the PdPt alloys via in situ X-ray absorption fine structure, Δμ analysis, identical location-electron microscopy and DFT calculations. We conclude that the origin of high activity and stability of the PdPt catalyst stems from the oxidation resistance of metallic Pt, forming mainly surface adsorbed O species at high potentials. Two stage degradation process are observed, showing an evolution of dynamic surface dependent ORR performance along with the deactivation process. The careful design of Pt alloy structure leads to controlled surface oxygen behaviours. This opens a new way to increase the lifespan of fuel cells and improve the Pt utilization efficiency

The effects of acute low-volume HIIT and aerobic exercise on leukocyte count and redox status

A single bout of exercise can result in inflammatory responses, increased oxidative stress and upregulation of enzymatic antioxidant mechanisms. Although low-volume high-intensity interval training (HIIT) has become popular, its acute responses on the above mechanisms have not been adequately studied. The present study evaluated the effects of HIIT on hematological profile and redox status compared with those following traditional continuous aerobic exercise (CET). Twelve healthy young men participated in a randomized crossover design under HIIT and CET. In HIIT session, participants performed four 30-sec sprints on a cycle-ergometer with 4 min of recovery against a resistance of 0.375 kg/kg of body mass. CET consisted of 30-min cycling on a cycle-ergometer at 70% of their VO2max. Blood was drawn at baseline, immediately post, 24h, 48h and 72h post-exercise and was analyzed for complete blood count and redox status (thiobarbituric acid reactive substances, [TBARS]; protein carbonyls, [PC]; total antioxidant capacity, [TAC]; catalase and uric acid). White blood cells (WBC) increased after both exercise protocols immediately post-exercise (HIIT: 50% and CET: 31%, respectively). HIIT increased (+22%) PC post-exercise compared to baseline and CET (p 0.05) for TBARS and catalase following either exercise protocol. Low-volume HIIT is associated with a greater acute phase leukocyte count and redox response than low-volume CET, and this should be considered when an exercise training program is developed and complete blood count is performed for health purposes

Disparate habitual physical activity and dietary intake profiles of elderly men with low and elevated systemic inflammation

The development of chronic, low-grade systemic inflammation in the elderly (inflammaging) has been associated with increased incidence of chronic diseases, geriatric syndromes, and functional impairments. The aim of this study was to examine differences in habitual physical activity (PA), dietary intake patterns, and musculoskeletal performance among community-dwelling elderly men with low and elevated systemic inflammation. Nonsarcopenic older men free of chronic diseases were grouped as ‘low’ (LSI: n = 17; 68.2 ± 2.6 years; hs-CRP: 1 mg/L) systemic inflammation according to their serum levels of high-sensitivity CRP (hs-CRP). All participants were assessed for body composition via Dual Emission X-ray Absorptiometry (DEXA), physical performance using the Short Physical Performance Battery (SPPB) and handgrip strength, daily PA using accelerometry, and daily macro- and micronutrient intake. ESI was characterized by a 2-fold greater hs-CRP value than LSI (p < 0.01). The two groups were comparable in terms of body composition, but LSI displayed higher physical performance (p < 0.05), daily PA (step count/day and time at moderate-to-vigorous PA (MVPA) were greater by 30% and 42%, respectively, p < 0.05), and daily intake of the antioxidant vitamins A (6590.7 vs. 4701.8 IU/day, p < 0.05), C (120.0 vs. 77.3 mg/day, p < 0.05), and E (10.0 vs. 7.5 mg/day, p < 0.05) compared to ESI. Moreover, daily intake of vitamin A was inversely correlated with levels of hs-CRP (r = −0.39, p = 0.035). These results provide evidence that elderly men characterized by low levels of systemic inflammation are more physically active, spend more time in MVPA, and receive higher amounts of antioxidant vitamins compared to those with increased systemic inflammation

Traumatic bone cyst of the mandible of possible iatrogenic origin: a case report and brief review of the literature

The traumatic bone cyst (TBC) is an uncommon nonepithelial lined cavity of the jaws. The lesion is mainly diagnosed in young patients most frequently during the second decade of life. The majority of TBCs are located in the mandibular body between the canine and the third molar. Clinically, the lesion is asymptomatic in the majority of cases and is often accidentally discovered on routine radiological examination usually as an unilocular radiolucent area with a "scalloping effect". The definite diagnosis of traumatic cyst is invariably achieved at surgery. Since material for histologic examination may be scant or non-existent, it is very often difficult for a definite histologic diagnosis to be achieved. We present a well documented radiographically and histopathologically atypical case of TBC involving the ramus of the mandible, which is also of possible iatrogenic origin. The literature is briefly reviewed

Lipoprotein-Associated Phospholipase A2: A Novel Contributor in Sjögren’s Syndrome-Related Lymphoma?

BackgroundB-cell non-Hodgkin’s lymphoma (B-NHL) is one of the major complications of primary Sjögren’s syndrome (SS). Chronic inflammation and macrophages in SS minor salivary glands have been previously suggested as significant predictors for lymphoma development among SS patients. Lipoprotein-associated phospholipase A2 (Lp-PLA2)—a product mainly of tissue macrophages—is found in the circulation associated with lipoproteins and has been previously involved in cardiovascular, autoimmune, and malignant diseases, including lymphoma.ObjectiveThe purpose of the current study was to investigate the contributory role of Lp-PLA2 in B-NHL development in the setting of primary SS.MethodsLp-PLA2 activity in serum samples collected from 50 primary SS patients with no lymphoma (SS-nL), 9 primary SS patients with lymphoma (SS-L), and 42 healthy controls (HC) was determined by detection of [3H]PAF degradation products by liquid scintillation counter. Moreover, additional sera from 50 SS-nL, 28 SS-L, and 32 HC were tested for Lp-PLA2 activity using a commercially available ELISA kit. Lp-PLA2 mRNA, and protein expression in minor salivary gland (MSG) tissue samples derived from SS-nL, SS-L patients, and sicca controls (SC) were analyzed by real-time PCR, Western blot, and immunohistochemistry.ResultsSerum Lp-PLA2 activity was significantly increased in SS-L compared to both SS-nL and HC by two independent methods implemented [mean ± SD (nmol/min/ml): 62.0 ± 13.4 vs 47.6 ± 14.4 vs 50.7 ± 16.6, p-values: 0.003 and 0.04, respectively, and 19.4 ± 4.5 vs 15.2 ± 3.3 vs 14.5 ± 3.0, p-values: &lt;0.0001, in both comparisons]. ROC analysis revealed that the serum Lp-PLA2 activity measured either by radioimmunoassay or ELISA has the potential to distinguish between SS-L and SS-nL patients (area under the curve [AUC]: 0.8022, CI [95%]: 0.64–0.96, p-value: 0.004 for radioimmunoassay, and AUC: 0.7696, CI [95%]: 0.66–0.88, p-value: &lt;0.0001, for ELISA). Lp-PLA2 expression in MSG tissues was also increased in SS-L compared to SS-nL and SC at both mRNA and protein level. ROC analysis revealed that both MSG mRNA and protein Lp-PLA2 have the potential to distinguish between SS-nL and SS-L patients (area under the curve [AUC] values of 0.8490, CI [95%]: 0.71–0.99, p-value: 0.0019 and 0.9444, CI [95%]: 0.79–1.00, p- value: 0.0389 respectively). No significant difference in either serum Lp-PLA2 activity or MSG tissue expression was observed between SS-nL and HC.ConclusionsLp-PLA2 serum activity and MSG tissue mRNA/protein expression could be a new biomarker and possibly a novel therapeutic target for B-cell lymphoproliferation in the setting of SS

Nrf2-interacting nutrients and COVID-19 : time for research to develop adaptation strategies

There are large between- and within-country variations in COVID-19 death rates. Some very low death rate settings such as Eastern Asia, Central Europe, the Balkans and Africa have a common feature of eating large quantities of fermented foods whose intake is associated with the activation of the Nrf2 (Nuclear factor (erythroid-derived 2)-like 2) anti-oxidant transcription factor. There are many Nrf2-interacting nutrients (berberine, curcumin, epigallocatechin gallate, genistein, quercetin, resveratrol, sulforaphane) that all act similarly to reduce insulin resistance, endothelial damage, lung injury and cytokine storm. They also act on the same mechanisms (mTOR: Mammalian target of rapamycin, PPAR gamma:Peroxisome proliferator-activated receptor, NF kappa B: Nuclear factor kappa B, ERK: Extracellular signal-regulated kinases and eIF2 alpha:Elongation initiation factor 2 alpha). They may as a result be important in mitigating the severity of COVID-19, acting through the endoplasmic reticulum stress or ACE-Angiotensin-II-AT(1)R axis (AT(1)R) pathway. Many Nrf2-interacting nutrients are also interacting with TRPA1 and/or TRPV1. Interestingly, geographical areas with very low COVID-19 mortality are those with the lowest prevalence of obesity (Sub-Saharan Africa and Asia). It is tempting to propose that Nrf2-interacting foods and nutrients can re-balance insulin resistance and have a significant effect on COVID-19 severity. It is therefore possible that the intake of these foods may restore an optimal natural balance for the Nrf2 pathway and may be of interest in the mitigation of COVID-19 severity