Ferrosilicate-Based Heterogeneous Fenton Catalysts: Influence of Crystallinity, Porosity, and Iron Speciation

Different ferrosilicate samples have been prepared with varying degrees of crystallinity, porous texture, and speciation of the Fe sites by both hydrothermal and sol–gel procedures: Fe-silicalite-1 with microcrystals (2–10 µm) and nanocrystals (180 nm), Fe-containing composite material consisting of silicalite-1 and amorphous silica, and two samples of mesoporous Fe-containing amorphous silica Fe–SiO2. The resulting solids have been tested for their potential as organic pollutants removal under Fenton-like conditions in heterogeneous catalytic wet peroxide oxidation of phenol and clarithromycin lactobionate. Our results indicate that the three aforementioned parameters show a strong interplay towards the abatement of pollutants in liquid phase. Thus, samples with high crystallinity show an improved performance in the oxidation of organic contaminants over amorphous samples in which the Fe speciation is very well controlled.The work was financially supported by the Ministry of Education and Science of the Russian Federation (RFMEFI60417 X 0159, title of the agreement: “Development of methods for hydrotreating of vacuum residue into high-quality marine fuels on macroporous catalysts”). The authors from Spanish side thank the Spanish Ministry of Economy and Competitiveness (MINECO), Generalitat Valenciana and FEDER (CTQ2015-66080-R MINECO/FEDER and PROMETEOII/2014/010) for financial support. J.G.A. thanks the Spanish Ministry of Economy and Competitiveness (MINECO) for his fellowship (BES-2013-063678)

Self-propagating High-temperature Synthesis of Materials Based on Tungsten Carbide for One-Pot Hydrolysis-Hydrogenolysis of Cellulose Into Ethylene Glycol and 1,2-Propylene Glycol

Методом самораспространяющегося высокотемпературного синтеза из смеси оксида вольфрама, металлического магния, технического углерода и CaCO3 с использованием механохимической обработки получены каталитические системы на основе карбида вольфрама (WnC), содержащие преимущественно W2C. Показано, что фазовый состав образующихся материалов зависит от количества CaCO3. Каталитические свойства полученных материалов исследованы в реакции гидролиза-гидрогенолиза целлюлозы до низших полиолов (этиленгликоль (ЭГ) и 1,2-пропиленгликоль (ПГ)). Установлено, что в присутствии WnC основными продуктами реакции являются ЭГ и ПГ с соотношением ПГ/ЭГ – 1,5-1,8. Нанесение наночастиц никеля на поверхность WnC материалов повышает скорость реакции и выход целевых продуктов. Максимальный суммарный выход диолов составил 47,1 мол. %Catalytic systems based on tungsten carbide (WnC) containing mainly W2C were obtained by the method of self-propagating high-temperature synthesis from a mechanochemically activated mixture of tungsten oxide, metallic magnesium, carbon black and CaCO3. The phase composition of the formed materials was shown to depend on the amount of CaCO3. The catalytic properties of the materials were tested in the hydrolysis-hydrogenation of cellulose to ethylene glycol (EG) and 1,2-propylene glycol (PG). It was established that in the presence of WnC the main products of the reaction were EG and PG with a ratio of PG/EG – 1.5-1.8. The deposition of nickel nanoparticles on the WnC surface increased the reaction rate and product yields. The maximum total yield of diols was 47.1 mol. %

Antiinflammatory Therapy with Canakinumab for Atherosclerotic Disease

Background: Experimental and clinical data suggest that reducing inflammation without affecting lipid levels may reduce the risk of cardiovascular disease. Yet, the inflammatory hypothesis of atherothrombosis has remained unproved. Methods: We conducted a randomized, double-blind trial of canakinumab, a therapeutic monoclonal antibody targeting interleukin-1β, involving 10,061 patients with previous myocardial infarction and a high-sensitivity C-reactive protein level of 2 mg or more per liter. The trial compared three doses of canakinumab (50 mg, 150 mg, and 300 mg, administered subcutaneously every 3 months) with placebo. The primary efficacy end point was nonfatal myocardial infarction, nonfatal stroke, or cardiovascular death. RESULTS: At 48 months, the median reduction from baseline in the high-sensitivity C-reactive protein level was 26 percentage points greater in the group that received the 50-mg dose of canakinumab, 37 percentage points greater in the 150-mg group, and 41 percentage points greater in the 300-mg group than in the placebo group. Canakinumab did not reduce lipid levels from baseline. At a median follow-up of 3.7 years, the incidence rate for the primary end point was 4.50 events per 100 person-years in the placebo group, 4.11 events per 100 person-years in the 50-mg group, 3.86 events per 100 person-years in the 150-mg group, and 3.90 events per 100 person-years in the 300-mg group. The hazard ratios as compared with placebo were as follows: in the 50-mg group, 0.93 (95% confidence interval [CI], 0.80 to 1.07; P = 0.30); in the 150-mg group, 0.85 (95% CI, 0.74 to 0.98; P = 0.021); and in the 300-mg group, 0.86 (95% CI, 0.75 to 0.99; P = 0.031). The 150-mg dose, but not the other doses, met the prespecified multiplicity-adjusted threshold for statistical significance for the primary end point and the secondary end point that additionally included hospitalization for unstable angina that led to urgent revascularization (hazard ratio vs. placebo, 0.83; 95% CI, 0.73 to 0.95; P = 0.005). Canakinumab was associated with a higher incidence of fatal infection than was placebo. There was no significant difference in all-cause mortality (hazard ratio for all canakinumab doses vs. placebo, 0.94; 95% CI, 0.83 to 1.06; P = 0.31). Conclusions: Antiinflammatory therapy targeting the interleukin-1β innate immunity pathway with canakinumab at a dose of 150 mg every 3 months led to a significantly lower rate of recurrent cardiovascular events than placebo, independent of lipid-level lowering. (Funded by Novartis; CANTOS ClinicalTrials.gov number, NCT01327846.

Heterogeneous Biocatalysts Prepared by Immuring Enzymatic Active Components inside Silica Xerogel and Nanocarbons-In-Silica Composites

Proprietary results on preparation and studies of whole-cell and lysates-based heterogeneous biocatalysts with different enzymatic activity were reviewed. A peculiar method was developed for preparing these biocatalysts by immuring (entrapping) enzymatic active components (EAC) inside silica (SiO2) xerogel and nanocarbons-in-silica composites. Properties of the multi-component composite biocatalysts such as enzymatic activity and operational stability were compared. The effect of the inclusion of nanocarbons such as nanotubes, nanofibers, and onion-like nanospheres with various texture, nanostructure and dispersion were thoroughly studied. With invertase-active biocatalysts, the direct correlation between an increase in the enzymatic activity of the nanocarbons-in-silica biocatalyst and efficiency of EAC adhesion on nanocarbons was observed. The steady-state invertase activity of the baker yeast lysates-based biocatalysts was determined to increase by a factor of 5–6 after inclusion of the multi-walled carbon nanotubes inside SiO2-xerogel. With lipase-active biocatalysts, the effect of the included nanocarbons on the biocatalytic properties depended significantly on the reaction type. In interesterification of oil-fat blends, the biocatalysts without any included nanocarbons demonstrated the maximal lipase activity. In esterification of fatty acids with aliphatic alcohols, the activity of the biocatalysts increased by a factor of 1.5–2 after inclusion of the aggregated multi-walled carbon nanotubes (CNTs) inside SiO2-xerogel. In the low-temperature synthesis of isopentyl esters of butyric (C4:0), capric (C10:0), and srearic (C18:0) fatty acids, the lipase-active composite CNTs-in-silica biocatalysts operated without loss of activity for more than thousand hours