Efficacy of Anakinra in Refractory Adult-Onset Still's Disease: Multicenter Study of 41 Patients and Literature Review

Adult-onset Still's disease (AOSD) is often refractory to standard therapy. Anakinra (ANK), an interleukin-1 receptor antagonist, has demonstrated efficacy in single cases and small series of AOSD. We assessed the efficacy of ANK in a series of AOSD patients. Multicenter retrospective open-label study. ANK was used due to lack of efficacy to standard synthetic immunosuppressive drugs and in some cases also to at least 1 biologic agent. Forty-one patients (26 women/15 men) were recruited. They had a mean age of 34.4 ± 14 years and a median [interquartile range (IQR)] AOSD duration of 3.5 [2-6] years before ANK onset. At that time the most common clinical features were joint manifestations 87.8%, fever 78%, and cutaneous rash 58.5%. ANK yielded rapid and maintained clinical and laboratory improvement. After 1 year of therapy, the frequency of joint and cutaneous manifestations had decreased to 41.5% and to 7.3% respectively, fever from 78% to 14.6%, anemia from 56.1% to 9.8%, and lymphadenopathy from 26.8% to 4.9%. A dramatic improvement of laboratory parameters was also achieved. The median [IQR] prednisone dose was also reduced from 20 [11.3-47.5] mg/day at ANK onset to 5 [0-10] at 12 months. After a median [IQR] follow-up of 16 [5-50] months, the most important side effects were cutaneous manifestations (n = 8), mild leukopenia (n = 3), myopathy (n = 1), and infections (n = 5). ANK is associated with rapid and maintained clinical and laboratory improvement, even in nonresponders to other biologic agents. However, joint manifestations are more refractory than the systemic manifestations

Microstructural studies of HDS catalytic nanomaterials

Trabajo presentado en International Multidisciplinary Joint Meeting - Nanoscience and Condensed Matter Physics, celebrado en Morelia (México) del 15 al 17 de mayo de 2013.The siliceous SBA-15 and SBA-16 materials were used as a support for ternary Co(Ni)MoW sulfide hydrotreating catalysts. This work presents the microstructural study of the nanostructurated materials, obtained from HRTEM images and X-ray diffraction analysis. The catalyst activity was evaluated in the hydrodesulfurization (HDS) of dibenzothiophene (DBT) performed in a batch reactor at 350 °C and total pressure of 3.1 MPa. It was found that both the morphology of the support and its modification with varying amounts of phosphorous affected the catalytic activity of the materials in HDS of DBT reaction.Peer Reviewe

Characterization and HDS performance of sulfided CoMoW catalysts supported on mesoporous Al-SBA-16 substrates

In this work, the catalytic activity of ternary Co–Mo–W/Al-SBA-16 systems was investigated in the reaction of hydrodesulfurization (HDS) of dibenzothiophene (DBT) performed in a batch reactor at 350 °C and total H2 pressure of 33.8 bar. The synthesized materials were characterized by a variety of techniques (chemical analysis, N2 adsorption–desorption isotherms, XRD, TPR, TPD-NH3, FTIR of adsorbed pyridine, DRS-UV–vis, HRTEM and XPS). By applying the direct synthesis method, high surface area substrates with Al3+ incorporated into the silica framework. The activity results indicate that all CoMoW/Al-SBA-16 catalysts were active in the HDS of DBT, the largest activity was found in the catalyst with the highest Al-content. This behavior was explained in terms of its largest specific area and good dispersion of the metal sulfide phases having average size of 3.3 nm (from HRTEM). Moreover, FT-IR spectroscopic study of adsorbed pyridine indicated Al incorporation into a SBA-16 substrate produces both Brønsted and Lewis acidities, which are beneficial for the HDS of DBT. All catalysts showed a high selectivity towards biphenyl indicating that HDS of DBT reaction proceeds mainly via direct desulfurization (DDS) reaction pathway.Financial supports from the Scientific Cooperation FONCICYT Program (FONCICYT-96194 project), the Spanish Ministry of Science and Innovation (ENE2010-15387-C02-01) and the Community of Madrid (S2009ENE-1743) projects are gratefully acknowledged. R. Huirache-Acuña thanks the support of CONACYT 182191, PROMEP PTC-273 and CIC UMSNH 2013 and 2014 Projects.Peer Reviewe

Enhancement of phenol hydrodeoxygenation over Pd catalysts supported on mixed HY zeolite and Al2O3. An approach to O-removal from bio-oils

This contribution describes the effect of the support (zeolite ultrastable HY, alumina (Al) and mixed HY–Al carriers) on the catalytic activity of Pd catalysts in the phenol hydrodeoxygenation (HDO) reaction carried out in a flow fixed-bed reactor at T = 523–573–623 K, P = 15 bar and WHSV = 0.5 h−1. Phenol dissolved in n-octane was used as model compound of bio-oil species derived from fast pyrolysis of lignocellulosic biomass. The catalysts were characterized by N2 physisorption, XRD, TPR, TPD-NH3, DRIFT spectroscopy of adsorbed CO, HRTEM, X-ray photoelectron spectroscopy (XPS) and TPO/TGA techniques. The largest phenol conversion (63%) achieved at 523 K over the reduced Pd/20%HY–Al catalyst was similar to that obtained on a commercial NiMo/Al2O3–zeolite hydrocracking sample (HCK) activated by sulfidation. Regardless of the reaction temperature, the only products detected in the HDO of phenol over all catalysts studied were four O-free compounds: benzene, cyclohexene, cyclohexane, and methylcylopentene. Both reduced Pd/20%HY–Al and sulfided commercial HCK catalysts produced similar yields of O-free products. From the catalyst activity-structure correlation, it can be concluded that the HDO of phenol is favoured on the bifunctional Pd/20%HY–Al catalyst which possesses moderate acidity and improved Pd dispersion on the support surface. The contributions of the acid sites to the catalyst activity and deactivation by coke are discussed.Financial support by the Community of Madrid (Spain) and European Union (Project S2009/ENE-1743) is gratefully acknowledged. S.E. acknowledges financial support from the Spanish Ministry of Science and Innovation (ENE2010-21198-C04-03) and the Basque Autonomous Government (IE09-263-IE10-288-VALCAPEF).N

Effect of Ir and Pt addition on the HDO performance of RuS2/SBA-15 sulfide catalysts

Ir and Pt have been tested as dopants for ruthenium sulfide supported on ordered SBA-15 mesoporous silica. The incorporation of Ir or Pt into RuS2/SBA-15 was found to enhance the activity in the gas-phase hydrodeoxygenation (HDO) of phenol carried out at 310 °C and 30 bar of total H2 pressure. X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy, temperature programmed desorption of NH3 and H2-temperature-programmed reduction of the sulfided catalysts were used to characterize the catalysts. XPS analysis of the spent catalysts confirmed the oxidation of ruthenium sulfide during HDO of phenol. The main factor that influences the catalyst activity was the surface exposure of the active phases, whereas the formation of oxysulfide species did not inhibit the HDO reaction.Thanks to MICINN for funding CTQ2012-37925-C03-03 and FEDER Projects, and Project of Excellence RNM 1565 of Junta de Andalucía for financial support. This study is also partially supported by the MICINN (ENE2007-67533-C02-01 Project) and CAM (S2009ENE-1743 Project).Peer Reviewe

HDS performance of sulfided CoMoW/Al-SBA-16 catalysts

Trabajo presentado en el International Mexican Congress on Chemical Reaction Engineering, celebrado en Acapulco (México) del 07 al 13 de junio de 2014.In this work, the catalytic activity of ternary Co-Mo-W/Al-SBA-16 systems was investigated in the reaction of hydrodesulfurization (HDS) of dibenzothiophene (DBT) performed in a batch reactor at 350 °C and total H2 pressure of 33.8 bar. The synthetized materials were characterized by a variety of techniques (chemical analysis, N2 adsorption¿desorption isotherms, XRD, TPR, TPD-NH3, FTIR of adsorbed pyridine, DRS-UV-vis, HRTEM and XPS). By applying the direct synthesis method, high surface area substrates with Al3+ incorporated in the lattice and a small quantity of Brønsted acid sites were obtained. The activity results indicate that all CoMoW/Al-SBA-16 catalysts were active in the HDS of DBT, the largest activity was found in the catalyst with the highest Al-content. This behavior was explained in terms of its largest specific area, good dispersion of the metal sulfide phases having average size of 3.3 nm and the presence of small amount of Brønsted acid sites. All catalysts showed a high selectivity towards biphenyl indicating that HDS of DBT reaction proceeds mainly on the metal sites via direct desulfurization (DDS) reaction pathway.Peer Reviewe

Structure and Reactivity of sol–gel V/SiO2 Catalysts for the Direct Conversion of Methane to Formaldehyde

[EN] Vanadium oxide-silica catalysts prepared by the sol–gel method were characterized by different techniques (nitrogen adsorption–desorption isotherms, scanning electron microscopy, X-ray diffraction, temperature-programmed reduction, Raman spectroscopy and X-ray photoelectron spectroscopy) and applied in the direct conversion of methane to C1 oxygenates. The addition of a small amount of nitric oxide to the reaction mixture reduced the energy barrier for H-abstraction, increasing the methane conversion and formaldehyde yield. Correlations between the characterization and activity results indicate that the reaction occurs on tetrahedrally coordinated vanadium sites, as the maximum formaldehyde yield was found for the catalyst with a vanadium content of 1.5 wt%, which has a high surface density of well-dispersed tetrahedrally coordinated monomeric or slightly oligomerized VO species. On the other hand, a high space velocity and CH:O ratio decrease the subsequent oxidation to carbon oxides, increasing oxygenate formation.This work was supported by Najran University, Najran, The Kingdom of Saudi Arabia. This is a post-peer-review, pre-copyedit version of an article published in Topics in Catalysis. The final authenticated version is available online at: http://dx.doi.org/10.1007/s11244-017-0809-

Sulfated CexZr1−xO2 oxides. Surface properties and performance for methane oxidation under fuel-rich conditions

Two series of sulfated zirconia-ceria based catalysts have been prepared by coprecipitation of the Zr and Ce salts, which were then sulfated by impregnation using HSO and [(NH)SO] and calcined at 650 °C for 4 h. The sulfated and persulfated Zr-Ce-O samples were synthesized with Zr/Ce ratios ranging from 1 to 15. The textural, structural and surface characteristics of the resulting modified catalysts were determined by N adsorption-desorption, XRD, XPS spectroscopy and TPD of NH, and results were related to their catalytic behaviour. The catalysts were tested in the direct conversion of methane at high temperature (650 °C) under fuel-rich conditions to obtain C oxygenates (CHOH and HCHO). Experiments were conducted using low O/CH ratio mixtures and high space velocity. It was shown that O/CH feeds resulted in practically total combustion of CH when sulfated/persulfated ceria-zirconia catalysts are used, while the nature of the different phases modifies the surface acidity, which plays a crucial role on the extent of deep oxidation reactions.This work was supported by Najran University, Najran, The Kingdom of Saudi Arabi