Experimental and numerical investigation of supported rhodium catalysts for partial oxidation of methane in exhaust gas diluted reaction mixtures

The partial oxidation of methane/oxygen mixtures with large exhaust gas dilution (46.3 vol% H₂O and 23.1 vol% CO₂) has been investigated experimentally and numerically over Rh/CeO₂-ZrO₂, Rh/ZrO₂ and Rh/α-Al₂O₃ catalysts. Experiments were carried out in a short-contact-time reactor at 5 bar and included exhaust gas analysis, temperature measurements along the reactor, and catalyst characterization. Additional experiments were performed in an optically accessible channel-flow reactor and involved in situ Raman measurements of major gas-phase species concentrations over the catalyst boundary layer and laser-induced fluorescence (LIF) of formaldehyde. A full elliptic two-dimensional numerical code that included elementary hetero-/homogeneous chemical reaction schemes and relevant heat transfer mechanisms in the solid was used in the simulations. The employed heterogeneous reaction mechanism, including only active Rh sites, reproduced the experiments with good accuracy. The ratio of active to geometrical surface area, deduced from hydrogen chemisorption measurements, was the single model parameter needed to account for the effect of different supports. This indicated that water activation occurring on support sites, resulting in inverse OH spillover from the support to the noble metal sites, could be neglected under the present conditions with high water dilution. An evident relationship between noble metal dispersion and catalytic behavior, in terms of methane conversion and synthesis gas yields, could be established. Both measurements and predictions indicated that an increasing Rh dispersion (in the order Rh/α-Al₂O₃, Rh/ZrO₂, and Rh/CeO₂-ZrO₂) resulted in higher methane conversions, lower surface temperatures, and higher synthesis gas yields.     

High Mutational Heterogeneity,and New Mutations in the Human Coagulation Factor V Gene. Future Perspectives for Factor V Deficiency Using Recombinant and Advanced Therapies

Factor V is an essential clotting factor that plays a key role in the blood coagulation cascade on account of its procoagulant and anticoagulant activity. Eighty percent of circulating factor V is produced in the liver and the remaining 20% originates in the α-granules of platelets. In humans, the factor V gene is about 80 kb in size; it is located on chromosome 1q24.2, and its cDNA is 6914 bp in length. Furthermore, nearly 190 mutations have been reported in the gene. Factor V deficiency is an autosomal recessive coagulation disorder associated with mutations in the factor V gene. This hereditary coagulation disorder is clinically characterized by a heterogeneous spectrum of hemorrhagic manifestations ranging from mucosal or soft-tissue bleeds to potentially fatal hemorrhages. Current treatment of this condition consists in the administration of fresh frozen plasma and platelet concentrates. This article describes the cases of two patients with severe factor V deficiency, and of their parents. A high level of mutational heterogeneity of factor V gene was identified, nonsense mutations, frameshift mutations, missense changes, synonymous sequence variants and intronic changes. These findings prompted the identification of a new mutation in the human factor V gene, designated as Jaén-1, which is capable of altering the procoagulant function of factor V. In addition, an update is provided on the prospects for the treatment of factor V deficiency on the basis of yet-to-be-developed recombinant products or advanced gene and cell therapies that could potentially correct this hereditary disorder.     

Decellularised Human Umbilical Artery as a Vascular Graft Elicits Minimal Pro-Inflammatory Host Response Ex Vivo and In Vivo

Small diameter (<6 mm) vessel grafts still pose a challenge for scientists worldwide. Decellularised umbilical artery (dUA) remains promising as small diameter tissue engineered vascular graft (TEVG), yet their immunogenicity remains unknown. Herein, we evaluated the host immune responses, with a focus on the innate part, towards human dUA implantation in mice, and confirmed our findings in an ex vivo allogeneic human setup. Overall, we did not observe any differences in the number of circulating white blood cells nor the number of monocytes among three groups of mice (1) dUA patch; (2) Sham; and (3) Mock throughout the study (day −7 to 28). Likewise, we found no difference in systemic inflammatory and anti-inflammatory cytokine levels between groups. However, a massive local remodelling response with M2 macrophages were observed in the dUA at day 28, whereas M1 macrophages were less frequent. Moreover, human monocytes from allogeneic individuals were differentiated into macrophages and exposed to lyophilised dUA to maximize an eventual M1 response. Yet, dUA did not elicit any immediate M1 response as determined by the absence of CCR7 and CXCL10. Together this suggests that human dUA elicits a minimal pro-inflammatory response further supporting its use as a TEVG in an allogeneic setup.     

Optimal Sizing of a DBD Ozone Generator Using Response Surface Modeling

Dielectric barrier discharge (DBD) reactors used as ozone generators are well known today and widely used for water treatment and air disinfection. The purpose of this article is to propose an experimental procedure based on the response surface modeling in order to optimize the geometrical dimensions of the cylindrical shape ozone generator, i.e., the discharge gap and the electrodes length. Because an effective ozone generator is expected to give high ozone concentration with a minimum of power requirements, the applied high voltage was associated with the geometrical parameters to carry out a composite centered faces design. Obtained results indicate that for an efficient ozone generator, length of the electrodes needs to be optimized while the discharge gap should be minimized.     

Styrene butadiene rubber/epoxidized natural rubber/carbon filler nanocomposites: microstructural development and cure characterization

Microstructural development of elastomeric nanocomposites based on (50/50 wt%) styrene butadiene rubber (SBR) and epoxidized natural rubber (50 mol% epoxidation, ENR50) as the rubber matrix including two types of carbon fillers, carbon black (CB) and functionalized multiwall carbon nanotube (NH₂-MWCNT), which were prepared through melt mixing, was studied. The results from FTIR analysis show that there is interaction between functional groups on MWCNT surface and the rubber chains. The AFM analysis also indicates good dispersion of filler particles in the rubber phases. FESEM images from cryo-fractured surface of samples have revealed that nanotubes were rarely pulled out of matrix and their diameter increased, resulting from good interaction between MWCNTs and rubber chains. The DMA results confirm good interfacial interaction between them. Furthermore, the reduced difference between the two T_gs of phases (ΔT_g) shows that the incorporation of 3 phr MWCNT into the blend leads to increment in rubber phase compatibility but at higher MWCNT content (5 phr) due to lower Mooney viscosity of SBR phase, MWCNTs tend to remain in this phase. The bound rubber was adopted to characterize the polymer–filler interaction, showing that bound rubber content has an increasing trend with increasing in fillers content. The cure rheometric studies reveal that MWCNTs accelerate the cure process due to the presence of amine groups on the nanotube surface. In addition, the mechanical properties of samples show an increasing trend by increasing nano-filler content.

     

Analgesic,Anxiolytic and Anaesthetic Effects of Melatonin: New Potential Uses in Pediatrics

Exogenous melatonin is used in a number of situations, first and foremost in the treatment of sleep disorders and jet leg. However, the hypnotic, antinociceptive, and anticonvulsant properties of melatonin endow this neurohormone with the profile of a drug that modulates effects of anesthetic agents, supporting its potential use at different stages during anesthetic procedures, in both adults and children. In light of these properties, melatonin has been administered to children undergoing diagnostic procedures requiring sedation or general anesthesia, such as magnetic resonance imaging, auditory brainstem response tests and electroencephalogram. Controversial data support the use of melatonin as anxiolytic and antinociceptive agents in pediatric patients undergoing surgery. The aim of this review was to evaluate available evidence relating to efficacy and safety of melatonin as an analgesic and as a sedative agent in children. Melatonin and its analogs may have a role in antinociceptive therapies and as an alternative to midazolam in premedication of adults and children, although its effectiveness is still controversial and available data are clearly incomplete.     

Effects of various hydrocarbons on micellar growth

The effect of aliphatic and aromatic hydrocarbons on surfactant micellar growth has been investigated by viscosity measurements at 40°C. Aqueous and aqueous KBr (0.1 M) solutions of 0.1 M cetylpyridinium bromide (CPB) showed that the viscosity behavior changed substantially in the presence of KBr. This is attributed to favorable conditions produced by KBr that assist micellar growth by addition of hydrocarbons. Reasons for the effectiveness of the solubilized hydrocarbons are suggested and supported by theoretical arguments. The causes of viscosity decrease at higher aromatic hydrocarbon concentrations are also explained. Micellar growth with soluble aromatic/aliphatic hydrocarbons could also be initiated if a moderate salt concentration is present in CPB micellar solutions. The chainlength, solubilization site, and molar volume of the soluble hydrocarbons all affect the bulk viscosity of the solution. Such surfactant and hydrocarbon combinations may find use in micellar-enhanced ultrafiltration of benzene and its derivatives, but it should be kept in mind that micellar shape may change and be more curved at higher benzene derivative concentrations.     

Influence of Reaction Conditions on Diacid Formation During Au-Catalyzed Oxidation of Glycerol and Hydroxymethylfurfural

The selective oxidation of glycerol and 5-hydroxymethylfurfural (HMF) to diacids over supported gold catalysts (Au/C and Au/TiO₂) in liquid water at mild temperatures was a strong function of the added base such as NaOH. Use of hydrotalcite as a solid base in place of NaOH in the HMF reaction medium facilitated the production of diacid over Au/TiO₂, but extensive leaching of magnesium suggested that hydrotalcite was consumed stoichiometrically in the reaction. Production of diacids from glycerol oxidation over supported Au catalysts was promoted by operating in a continuous flow reactor and by increasing the catalyst loading in a semi-batch reactor. Trace inhibitors formed by conversion of the product monoacid are proposed to account for the generally low selectivity to diacids over gold catalysts.