Catalytic performance of Co3O4/CeO2 and Co3O4/CeO2–ZrO2 composite oxides for methane combustion: Influence of catalyst pretreatment temperature and oxygen concentration in the reaction mixture

The influence of catalyst pre-treatment temperature (650 and 750 °C) and oxygen concentration (λ = 8 and 1) on the light-off temperature of methane combustion has been investigated over two composite oxides, Co₃O₄/CeO₂ and Co₃O₄/CeO₂–ZrO₂ containing 30 wt.% of Co₃O₄. The catalytic materials prepared by the co-precipitation method were calcined at 650 °C for 5 h (fresh samples); a portion of them was further treated at 750 °C for 7 h, in a furnace in static air (aged samples).

Tests of methane combustion were carried out on fresh and aged catalysts at two different WHSV values (12 000 and 60 000 mL g⁻¹ h⁻¹). The catalytic performance of Co₃O₄/CeO₂ and Co₃O₄/CeO₂–ZrO₂ were compared with those of two pure Co₃O₄ oxides, a sample obtained by the precipitation method and a commercial reference. Characterization studies by X-ray diffraction (XRD), BET and temperature-programmed reduction (TPR) show that the catalytic activity is related to the dispersion of crystalline phases, Co₃O₄/CeO₂ and Co₃O₄/CeO₂–ZrO₂ as well as to their reducibility. Particular attention was paid to the thermal stability of the Co₃O₄ phase in the temperature range of 750–800 °C, in both static (in a furnace) and dynamic conditions (continuous flow). The results indicate that the thermal stability of the phase Co₃O₄ heated up to 800 °C depends on the size of the cobalt oxide crystallites (fresh or aged samples) and on the oxygen content (excess λ = 8, stoichiometric λ = 1) in the reaction mixture. A stabilizing effect due to the presence of ceria or ceria–zirconia against Co₃O₄ decomposition into CoO was observed.

Moreover, the role of ceria and ceria–zirconia is to maintain a good combustion activity of the cobalt composite oxides by dispersing the active phase Co₃O₄ and by promoting the reduction at low temperature.     

Thermal Poling of Soda‐Lime Silica Glass with Nonblocking Electrodes—Part 1: Effects of Sodium Ion Migration and Water Ingress on Glass Surface Structure

It is generally well known that not only the sodium itself, but also the non‐bridging oxygen (NBO) sites associated with sodium ions are largely responsible for the surface reactivity of soda‐lime‐silica (SLS) glass. Thermal poling can modify the distribution of sodium in the subsurface region. In this work, a commercial SLS float glass was thermally poled using nonblocking electrodes in air. The Na⁺?depleted anode surface and the Na⁺?gradient cathode surface were characterized using a variety of methods to find the compositional, structural and morphological effects of thermal poling. Of particular significance is the use of nondestructive vibrational spectroscopy methods, which can lead to new and improved understanding of water interactions with sodium and its sites in the glass. It was found that during thermal poling, the Na⁺?depleted glass network on the anode side undergoes condensation reactions of NBO sites accompanied by the increase in concentrations of silanol (SiOH) groups and molecular water species. In contrast, silanol and water species do not increase and the silicate network change is negligible in the Na⁺?gradient cathode side. Vibrational sum frequency generation (SFG) spectroscopy analysis revealed the difference in distributions of hydrous species in the Na⁺?depleted and Na⁺?gradient surfaces. The structural information of the thermally‐poled surfaces provides critical insights needed to understand the mechanical and mechanochemical properties of the Na⁺?concentration modified SLS glass surfaces reported in the Part 2 companion paper.     

Ionic Conductivity in Sodium–Alkaline Earth–Aluminosilicate Glasses

The effect of alkaline‐earth ions on Na transport in aluminosilicate glasses was studied by measuring ionic conductivity for a systematic compositional series of Na₂O–RO–Al₂O₃–SiO₂ glasses (R=Mg, Ca, Sr, Ba). The Na transport in aluminosilicate glass could be affected by compositional changes in aluminum coordination and nonbridging oxygen as well as physical properties such as dielectric constant, shear modulus, and ionic packing factor. Through careful experimental designs and measurements, the main determinants among these parameters were identified. ²⁷Al MAS‐NMR indicated that all aluminum species contained in these glasses are four‐coordinated. The activation energy for ion conductivity decreased with increasing aluminum content and decreasing ionic radii of the alkaline‐earth ion in the region where [Al] < [Na]. When the aluminum content exceeded the sodium content ([Al] > [Na]), the composition dependence of the activation energy depended on the specific alkaline earth. These results are explained based on variations in free volume and dielectric constant caused by structural changes around the AlO₄ charge compensation sites. These structure changes occur in response to the smaller size and higher field strength of the alkaline‐earth ions, and are most prevalent in the compositions which require bridging of two AlO₄ sites by the alkaline‐earth ion for charge compensation.     

Regulatory Noncoding and Predicted Pathogenic Coding Variants of CCR5 Predispose to Severe COVID-19

Genome-wide association studies (GWAS) found locus 3p21.31 associated with severe COVID-19. CCR5 resides at the same locus and, given its known biological role in other infection diseases, we investigated if common noncoding and rare coding variants, affecting CCR5, can predispose to severe COVID-19. We combined single nucleotide polymorphisms (SNPs) that met the suggestive significance level (P ≤ 1 × 10⁻⁵) at the 3p21.31 locus in public GWAS datasets (6406 COVID-19 hospitalized patients and 902,088 controls) with gene expression data from 208 lung tissues, Hi-C, and Chip-seq data. Through whole exome sequencing (WES), we explored rare coding variants in 147 severe COVID-19 patients. We identified three SNPs (rs9845542, rs12639314, and rs35951367) associated with severe COVID-19 whose risk alleles correlated with low CCR5 expression in lung tissues. The rs35951367 resided in a CTFC binding site that interacts with CCR5 gene in lung tissues and was confirmed to be associated with severe COVID-19 in two independent datasets. We also identified a rare coding variant (rs34418657) associated with the risk of developing severe COVID-19. Our results suggest a biological role of CCR5 in the progression of COVID-19 as common and rare genetic variants can increase the risk of developing severe COVID-19 by affecting the functions of CCR5.     

Anthocyanin composition and extractability in berry skin and wine of Vitis vinifera L. cv. Aglianico

BACKGROUND: The present article reports the anthocyanin content in the berry skin and wine of the Italian red grape cultivar Aglianico (clone VCR11 grafted onto 1103 Paulsen), one of the most ancient vines and famous for its deep‐red colour. Anthocyanins were extracted from frozen berry skin in an acidified methanol solution. The extraction mixtures, monitored for 120 h, were analysed by high‐performance liquid chromatography. RESULTS: The extraction from berry skin of delphinidin, petunidin and malvidin appeared to be a time‐independent process, whereas the concentration of peonidin increased linearly with time. Peonidin‐O‐acetyl‐glucoside was transferred from skin more slowly than petunidin‐O‐acetyl‐glucoside and malvidin‐O‐acetyl‐glucoside. The anthocyanin composition of the resulting wine showed that the total anthocyanin content was about one‐tenth of the corresponding berry skin content. The ratio acetyl/coumaroyl anthocyanins in the wine was sharply higher than the value in berry skin (0.85 and 0.10, respectively), indicating an enrichment of acetyl derivatives in the wine. CONCLUSION: Levels of single anthocyanins in wine were not always correlated with those detected in grapes, as they were affected by winemaking. The high values of some anthocyanins in Aglianico wine could ameliorate its quality, increasing the chromatic properties, aging stability and product acceptance. Copyright © 2011 Society of Chemical Industry     

Effect of loading‐unloading cycles on impact‐damaged jute/glass hybrid laminates

The production of glass/plant fiber hybrid laminates is a possibility for obtaining semistructural materials with sufficient impact properties, and a better life cycle analysis (LCA) profile than fiberglass. The simplest and possibly the most effective configuration for the production of these hybrids would involve the use of a plant fiber reinforced laminate as the core between two glass fiber reinforced laminates. A main limitation to the use of composites including plant fibers is that their properties may be significantly affected by the presence of damage, so that even the application of a low stress level can result in laminate failure. In particular, it is suggested that when loading is repeatedly applied and removed, residual properties may vary in an unpredictable way. In this work, E‐glass/jute hybrid reinforced laminates, impacted in a range of energies (10, 12.5, and 15 J), have been subjected to post‐impact cyclic flexural tests with a step loading procedure. This would allow evaluating the effect of damage dissipation offered by the plant fiber reinforced core. The tests have also been monitored by acoustic emission (AE), which has confirmed the existence of severe limitations to the use of this hybrid material when impacted at energies close to penetration. POLYM. COMPOS., 2009. © 2009 Society of Plastics Engineers     

Influence of Al2O3 on the performance of CeO2 used as catalyst in the direct carboxylation of methanol to dimethylcarbonate and the elucidation of the reaction mechanism

In this paper we show that modification of ceria by loading alumina strongly reduces the oxidation of methanol and the consequent reduction of Ce(IV) to Ce(III) with increase of both the life of the catalysts and their selectivity. The combination of surface techniques (XPS and BET) with structural techniques (XRD) has allowed a good characterisation of the working catalysts. Spectroscopic analyses (DRIFT and multinuclear solid state and solution NMR) have permitted the monitoring of the species formed on the surface of the catalyst and released from it. The formation of DMC takes place in successive steps such as (i) interaction of methanol with the catalyst surface with the formation of the surface-bound OCH₃; (ii) building on the catalyst surface of the hemicarbonate moiety [–OCH₃ → –OC(O)OCH₃]; and (iii) reaction of the latter with the gas-phase methanol to afford the organic carbonate.     

Chromium (VI) removal by methylated biomass of Spirulina platensis: The effect of methylation process

Biosorption of heavy metals is an interesting approach to treat industrial wastewaters by an environmentally friendly system. Spirulina platensis biomass, an effective biosorbent for cations, cannot be used to adsorb chromate due to its negatively charged surface close to neutral conditions; therefore, methylation of biomass was performed to increase its adsorption capacity under these conditions. Batch adsorption tests carried out varying both Cr(VI) and methylated biomass concentrations showed that 2–4 g l^?1 of biosorbent were able to remove Cr(VI) with efficiency ≥80%, while higher Cr(VI) levels (43–50 mg l^?1) showed low removal efficiency. The model of Langmuir was shown to describe the adsorption phenomenon better than the Freundlich one. The values of the overall adsorption capacity of methylated biomass suggested that increased biosorbent availability does not necessarily correspond to larger amount of adsorbed metal. FT-IR spectra of dried and methylated biomass of S. platensis allowed us monitoring the efficiency of the methylation process through the analysis of CH and COO^? vibrational stretching modes, taken as diagnostic of this process.     

Pullulan‐based films and coatings for food packaging: Present applications,emerging opportunities,and future challenges

Societal and industrial demands for lower environmental impact, cost effectiveness, and high‐performance goods and services are increasingly impacting the choice of technologies which are developed and deployed in consumer products. Like many other sectors, food packaging is moving to new technologies; the use of biopolymers is one of the most promising strategies toward an optimized use of traditional packaging materials (e.g., oil‐based plastics) without impairing the goal of extending shelf life. Among other food packaging materials, pullulan is attracting much attention due to its unique features. The goal of this review is to provide an overview of current and emerging applications of pullulan within the food packaging sector. In particular, the functional properties of interest for the food packaging industry will be discussed in light of the physicochemical attributes of this exopolysaccharide. Future challenges that may dictate the successful penetration of pullulan in the food packaging market are also outlined. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40539.     

Microwave-Hydrothermal Synthesis of Nanophase Ferrites

This paper reports the synthesis of technologically important ferrites such as ZnFe₂O₄, NiFe₂O₄, MnFe₂O₄, and CoFe₂O₄ by using novel microwave-hydrothermal processing. Nanophase ferrites with high surface areas, in the range of 72-247m²/g, have been synthesized in a matter of a few minutes at temperatures as low as 164°C. The rapid synthesis of nanophase ferrites via an acceleration of reaction rates under microwave-hydrothermal conditions is expected to lead to energy savings.