Tumor necrosis factor inhibitors in psoriatic arthritis.

INTRODUCTION: Psoriatic arthritis (PsA) is a chronic inflammatory disease that can result in significant disability. With the emergence of tumor necrosis factor inhibitors (TNFi), therapeutic outcomes in PsA have improved substantially. The clinical efficacy and the inhibition of radiographic progression demonstrated by TNFi have transformed the management of PsA. However, there is still an unmet need for a subset of patients who do not respond adequately to TNFi. Areas covered: This review provides an overview of the pharmacokinetics of TNFi, the efficacy of TNFi in PsA, and the role of immunogenicity of TNFi in the treatment of PsA. In addition, we address the use of TNFi in the setting of other medications utilized in the treatment of PsA and the potential future role of biosimilars. Expert commentary: Monoclonal antibodies exhibit complex and widely variable pharmacokinetics. The study of factors that can affect the pharmacokinetics, such as immunogenicity, is valuable to further define and understand the use of TNFi in PsA, especially in the subset of patients who do not respond adequately to these agents or lose effectiveness over time

Production of C-2/C-3 Oxygenates from Planar Copper Nitride-Derived Mesoporous Copper via Electrochemical Reduction of CO2

Electrochemical reduction of CO2 provides an opportunity to produce fuels and chemicals in a carbon-neutral manner, assuming that CO2 can be captured from the atmosphere. To do so requires efficient, selective, and stable catalysts. In this study, we report a highly mesoporous metallic Cu catalyst prepared by electrochemical reduction of thermally nitrided Cu foil. Under aqueous saturated CO2 reduction conditions, the Cu3N-derived Cu electrocatalyst produces virtually no CH4, very little CO, and exhibits a faradaic efficiency of 68% in C2+ products (C2H4, C2H5OH, and C3H7OH) at a current density of ∼18.5 mA cm-2 and a cathode potential of -1.0 V versus the reversible hydrogen electrode. Under these conditions, the catalyst produces more oxygenated products than hydrocarbons. We show that surface roughness is a good descriptor of catalytic performance. The roughest surface reached 98% CO utilization efficiency for C2+ product formation from CO2 reduction and the ratio of oxygenated to hydrocarbon products correlates with the degree of surface roughness. These effects of surface roughness are attributed to the high population of undercoordinated sites as well as a high pH environment within the mesopores and adjacent to the surface of the catalyst

Binder materials for the cathodes applied to self-stratifying membraneless microbial fuel cell

© 2018 The Authors The recently developed self-stratifying membraneless microbial fuel cell (SSM-MFC) has been shown as a promising concept for urine treatment. The first prototypes employed cathodes made of activated carbon (AC) and polytetrafluoroethylene (PTFE) mixture. Here, we explored the possibility to substitute PTFE with either polyvinyl-alcohol (PVA) or PlastiDip (CPD; i.e. synthetic rubber) as binder for AC-based cathode in SSM-MFC. Sintered activated carbon (SAC) was also tested due to its ease of manufacturing and the fact that no stainless steel collector is needed. Results indicate that the SSM-MFC having PTFE cathodes were the most powerful measuring 1617 μW (11 W·m−3 or 101 mW·m−2). SSM-MFC with PVA and CPD as binders were producing on average the same level of power (1226 ± 90 μW), which was 24% less than the SSM-MFC having PTFE-based cathodes. When balancing the power by the cost and environmental impact, results clearly show that PVA was the best alternative. Power wise, the SAC cathodes were shown being the less performing (≈1070 μW). Nonetheless, the lower power of SAC was balanced by its inexpensiveness. Overall results indicate that (i) PTFE is yet the best binder to employ, and (ii) SAC and PVA-based cathodes are promising alternatives that would benefit from further improvements

Selective Hydrogenation and Hydrodeoxygenation of Aromatic Ketones to Cyclohexane Derivatives Using a Rh@SILP Catalyst

Rhodium nanoparticles immobilized on an acid-free triphenylphosphonium-based supported ionic liquid phase (Rh@SILP(Ph3-P-NTf2)) enabled the selective hydrogenation and hydrodeoxygenation of aromatic ketones. The flexible molecular approach used to assemble the individual catalyst components (SiO2, ionic liquid, nanoparticles) led to outstanding catalytic properties. In particular, intimate contact between the nanoparticles and the phosphonium ionic liquid is required for the deoxygenation reactivity. The Rh@SILP(Ph3-P-NTf2) catalyst was active for the hydrodeoxygenation of benzylic ketones under mild conditions, and the product distribution for non-benzylic ketones was controlled with high selectivity between the hydrogenated (alcohol) and hydrodeoxygenated (alkane) products by adjusting the reaction temperature. The versatile Rh@SILP(Ph3-P-NTf2) catalyst opens the way to the production of a wide range of high-value cyclohexane derivatives by the hydrogenation and/or hydrodeoxygenation of Friedel–Crafts acylation products and lignin-derived aromatic ketones. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA

Selective hydrogenation of fluorinated arenes using rhodium nanoparticles on molecularly modified silica

The production of fluorinated cyclohexane derivatives is accomplished through the selective hydrogenation of readily available fluorinated arenes using Rh nanoparticles on molecularly modified silica supports (Rh@Si-R) as highly effective and recyclable catalysts. The catalyst preparation comprises grafting non-polar molecular entities on the SiO2 surface generating a hydrophobic environment for controlled deposition of well-defined rhodium particles from a simple organometallic precursor. A broad range of fluorinated cyclohexane derivatives was shown to be accessible with excellent efficacy (0.05-0.5 mol% Rh, 10-55 bar H2, 80-100 °C, 1-2 h), including industrially relevant building blocks. Addition of CaO as scavenger for trace amounts of HF greatly improves the recyclability of the catalytic system and prevents the risks associated to the presence of HF, without compromising the activity and selectivity of the reaction. © The Royal Society of Chemistry

In situ differentiation processes in Plio-Pleistocene basaltic flows of Southern Payenia, Provinces of Mendoza and La Pampa

En este trabajo se presentan los resultados obtenidos de estudios petrológicos realizados en estructuras de segregación alojadas en lavas basálticas emplazadas al sur de la Provincia Volcánica de Payenia. Se analizaron cuatro tipos morfológicos de estructuras: mantos, láminas y cilindros de vesículas y vesículas de segregación. El líquido residual que les dio origen fue segregado durante la cristalización del núcleo de la colada y migró a través de una malla cristalina gracias al mecanismo de gas filter-pressing. De acuerdo a un estudio previo, las estructuras aquí analizadas clasifican texturalmente en tres categorías: afíricas de grano grueso (subtipo A), afíricas de grano fino (subtipo B) y seriadas (subtipo C). Los datos obtenidos de los análisis puntuales de las principales fases minerales de las estructuras de segregación indican que las mismas presentan composiciones más diferenciadas que sus basaltos hospedantes. Esto se evidencia a partir del enriquecimiento en Si, Fe, Na y K y el empobrecimiento de Al, Ca y Mg en la mineralogía de las estructuras en relación a la del basalto, lo cual se interpreta como el resultado de un proceso de cristalización fraccionada in situ. Los cálculos geotermométricos arrojaron una temperatura de erupción del basalto hospedante de 1195 ± 71 ºC y de entre 996 y 1001 ± 71 ºC para la temperatura del liquidus del vidrio que compone la vesícula de segregación.In situ differentiation processes in Plio-Pleistocene basaltic flows of Southern Payenia, Provinces of Mendoza and La Pampa In this paper are presented the petrologic studies made on segregation structures found in basaltic lava flows from southern Payenia Volcanic Province. Four morphological types of structures were identified: thick vesicle sheets, thin vesicle sheets, vesicle cylinders and segregation vesicles. The residual liquid migrated through a crystal network driven by the gas filter-pressing mechanism. In agree with a previous work the segregation structures classified according to their texture as aphyric coarse-grained textured (A-subtype), aphyric fine-grained textured (B-subtype) and seriate textured (C-subtype). The chemical data obtained from the individual analyzes of main mineral phases of the segregation structures indicate that they present more differentiated compositions than their host basalts. This is mainly evidenced by the enrichment in Si, Fe, Na and K and the drop of Al, Ca and Mg values in the mineral association of the structures with regard to the mineral chemistry of the basalt, which is interpreted as the result of an in situ crystal fractionation process. From thermometric calculations it was estimated that the eruption temperature of the host basalt was 1195 ± 71 ºC. The liquidus temperature estimated for the glass that constitutes the segregation vesicle groundmass was between 996 and 1001 ± 71 °C.Fil: Bernardi, Mauro Ignacio. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Ciencias de la Tierra y Ambientales de La Pampa. Universidad Nacional de La Pampa. Facultad de Ciencias Exactas y Naturales. Instituto de Ciencias de la Tierra y Ambientales de La Pampa; ArgentinaFil: Bertotto, Gustavo Walter. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Ciencias de la Tierra y Ambientales de La Pampa. Universidad Nacional de La Pampa. Facultad de Ciencias Exactas y Naturales. Instituto de Ciencias de la Tierra y Ambientales de La Pampa; ArgentinaFil: Ponce, Alexis Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Ciencias de la Tierra y Ambientales de La Pampa. Universidad Nacional de La Pampa. Facultad de Ciencias Exactas y Naturales. Instituto de Ciencias de la Tierra y Ambientales de La Pampa; Argentin

Validation of the ST3x1 Step Test as an estimator of peak VO2 in adults with cardiovascular risk factors

Objective: To validate a tool for assessment and control of functional capacity and peak oxygen uptake. Methods: A transversal, correlational study was conducted in which 111 subjects (49.81 ± 11.16 years) were evaluated, their body mass index (BMI) was 31.42 ± 4.07, classified with moderate and high cardiovascular risk, according to the American Association of Cardiovascular and Pulmonary Rehabilitation. Its peak oxygen uptake was measured directly and also through the Step Test 3x1 (ST3x1). Results: Peak oxygen uptake in ST3x1 corresponded to 28.54 ml•kg-1•min-1 and direct measurement at 28.14 ml•kg-1•min-1, with a “strong positive” Pearson correlation r = 0.81, Student n/s p = 0.14 Conclusion: ST3x1 is a valid alternative to estimate peak oxygen uptake in the group studied, and can be used in mass public health physical activity programs

Self-stratifying microbial fuel cell: The importance of the cathode electrode immersion height

© 2018 The Author(s) Power generation of bioelectrochemical systems (BESs) is a very important electrochemical parameter to consider particularly when the output has to be harvested for practical applications. This work studies the effect of cathode immersion on the performance of a self-stratified membraneless microbial fuel cell (SSM-MFC) fuelled with human urine. Four different electrolyte immersion heights, i.e. 1/4, 2/4, 3/4 and fully submerged were considered. The SSM-MFC performance improved with increased immersion up to 3/4. The output dropped drastically when the cathode was fully submerged with the conditions becoming fully anaerobic. SSM-MFC with 3/4 submerged cathode had a maximum power output of 3.0 mW followed by 2.4 mW, 2.0 mW, and 0.2 mW for the 2/4, 1/4 and fully submerged conditions. Durability tests were run on the best performing SSM-MFC with 3/4 cathode immersed and showed an additional increase in the electrochemical output by 17% from 3.0 mW to 3.5 mW. The analysis performed on the anode and cathode separately demonstrated the stability in the cathode behaviour and in parallel an improvement in the anodic performance during one month of investigation

Scalability of self-stratifying microbial fuel cell: Towards height miniaturisation

© 2019 The Authors The scalability of bioelectrochemical systems is a key parameter for their practical implementation in the real-world. Up until now, only urine-fed self-stratifying microbial fuel cells (SSM-MFCs) have been shown to be scalable in width and length with limited power density losses. For practical reasons, the present work focuses on the scalability of SSM-MFCs in the one dimension that has not yet been investigated, namely height. Three different height conditions were considered (1 cm, 2 cm and 3 cm tall electrodes). The normalised power density of the 2 cm and 3 cm conditions were similar either during the durability test under a hydraulic retention time of ≈39 h (i.e. 15.74 ± 0.99 μW.cm −3 ) and during the polarisation experiments (i.e. 27.79 ± 0.92 μW.cm −3 ). Conversely, the 1 cm condition had lower power densities of 11.23 ± 0.07 μW.cm −3 and 17.73 ± 3.94 μW.cm −3 both during the durability test and the polarisation experiment, respectively. These results confirm that SSM-MFCs can be scaled in all 3 dimensions with minimal power density losses, with a minimum height threshold for the electrode comprised between 1 cm and 2 cm

Seasonal and Interannual Variability of Phytoplankton Abundance and Community Composition on the Central Coast of California

Variations in the abundance and composition of phytoplankton greatly impact ecosystem structure and function. Within the California Current System (CCS), phytoplankton community structure is tightly coupled to seasonal variability in wind-driven coastal upwelling, a process that drives changes in coastal water temperatures and nutrient concentrations. Based on approximately a decade (2008-2018) of weekly phytoplankton measurements, this study provides the first characterization of the seasonal and interannual variability of phytoplankton abundance and composition in San Luis Obispo (SLO) Bay, an understudied region within the CCS. Overall, the seasonality of phytoplankton in SLO Bay mirrored that of the larger CCS; diatoms dominated the community during the spring upwelling season, whereas dinoflagellates dominated the community during the fall relaxation period. While we observed considerable interannual variability among phytoplankton taxa, of particular note was the absence of a fall dinoflagellate-dominated period from 2010 through 2013, followed by the return of the fall dinoflagellate-dominated period in 2014. This compositional shift coincided with a major phase shift of both the Pacific Decadal Oscillation (PDO) and North Pacific Gyre Oscillation (NPGO). In addition to exerting a strong influence on the seasonality of phytoplankton community succession and transition between diatom- and dinoflagellate-dominated periods, the state of both the PDO and NPGO also influenced the extent to which environmental conditions (temperature and upwelling winds) could predict community type. These results highlight the importance of long-term datasets and the consideration of large-scale climate patterns when assessing local ecosystem dynamics