Effect of size and oxidation state of size-controlled rhodium nanoparticles on the aqueous-phase hydrodechlorination of 4-chlorophenol

Unsupported size-controlled Rh nanoparticles of different size and oxidation state were tested as catalysts models in aqueous phase hydrodechlorination (303-318K, 1atm) using 4-chlorophenol (4-CP) as target compound. A chemical reduction method was employed for the synthesis of the nanoparticles using methanol and poly(N-vinyl-2-pyrrolidone) (PVP) as reducing and capping agent, respectively. The size of Rh nanoparticles was in a narrow range (1.9-4.9nm) whereas Rhn+/Rh0 ratio values were found within a wide range (0.56-3.89).High 4-CP conversion values (c.a. 100%) were achieved at low Rh concentration (2.45·10-3gL-1). Phenol, cyclohexanone, cyclohexanol and traces of cyclohexane were identified as reaction products. A wide range of activity values (1.7-29.4mmolg-1min-1) were obtained, being equivalent to the measured in a previous work with unsupported Pd nanoparticles, in spite of the fact that Rh supported catalysts have generally been reported as less active than Pd ones in liquid phase hydrodechlorination. As the size of Rh nanoparticles decreased the activity increased reaching a maximum at 2.8nm, lower size values leading to a significant decrease of activity. A remarkable dependence of activity on the Rhn+/Rh0 ratio was found, thus a higher activity corresponded to a higher relative amount of zero-valent Rh in the nanoparticles samples. Regression models were developed in order to address the significance of nanoparticles size and oxidation state for the prediction of selectivity to cyclohexanone and cyclohexanol at varying reaction times. A crossed effect of particle size and Rhn+/Rh0 ratio was identified as a significant factor influencing the selectivityWe greatly appreciate financial support from the Spanish MCYT (CTQ2009-09983 and CTQ2012-32821) and CAM (REMTAVARES S-2009/AMB-1588). J.A. Baeza thanks to the Spanish MICINN a research grant (BES-2010-030059

Aqueous phase reforming of starch wastewater over Pt and Pt-based bimetallic catalysts for green hydrogen production

This work analyses the application of aqueous phase reforming (APR) for green hydrogen production from starch industry wastewater. This work reports for the first time on the direct conversion of a high molecular weight biomass polymer contained in wastewater in contrast to low molecular weight substrates mainly reported in the literature. The potential of this type of feedstock was evaluated by varying the starch source (rice, potato, sweet potato and cassava) and the type of catalyst (carbon supported Pt, PtRu, PtPd, PtRe and PtRh catalysts). In APR experiments at 220 °C with synthetic wastewater, PtRu/C and Pt/C catalysts achieved the highest H2 yield values, around 51 mmol H2 per g of organic carbon in the initial wastewater, close to 2.6 times higher than that reported in the literature of brewery wastewater, a promising substrate. The lack of free aldehyde or keto groups due to glycosidic bonds between glucose units in starch results in higher conversion to gas and H2 production compared to APR of glucose. This fact shows that APR has more feedstock flexibility than that previously reported for light compounds. In the experiments with real wastewaters, the organic matter removal was influenced largely by the starch source: the best APR performance (28.5 mmol H2 gTOCi−1) was obtained for rice processing wastewater, which is characterized by the highest starch concentration and the lowest protein content. Poor performance was observed in the APR of potato processing wastewater, probably due to catalyst deactivation caused by protein fractio

Effect of structural ordering of the carbon support on the behavior of Pd catalysts in aqueous-phase hydrodechlorination

Catalysts consisting of Pd supported on virgin and heat-treated carbon blacks (homemade and commercial), graphites (natural and synthetic) and commercial carbon nanofibers were prepared and tested in the aqueous phase hydrodechlorinaton (HDC) of 4-chlorophenol (4-CP) under near ambient conditions (30 °C, 1 atm) in order to explore the effect of the support on the catalytic behavior. The homemade graphitized supports were prepared from commercial carbon black (CB) and from a carbon black-like material (CBPE) obtained from pyrolysis of low-density polyethylene. All the catalysts prepared yielded complete 4-CP conversion, although a wide range of activity was observed (10.7–173.5 mmol gPd−1 min−1). The graphitized carbon black provided the most active catalysts, showing Pd nanoparticles around 3 nm in size and a well-balanced contribution of Pd species (Pdn+/Pd0 = 0.9). Substantial differences of activity were found between the graphitized and not graphitized supports, even for catalysts with similar Pd nanoparticle size. The higher activity of the catalysts with graphitized supports can be partly associated to a more balanced initial Pdn+ to Pd0 ratio. Moreover, higher selectivity to hydrogenation products (cyclohexanone) was also achieved with those catalysts due to a higher contribution of the Pd0 speciesThe authors greatly appreciate financial support from the Spanish MINECO (CTQ2012-32821

Autoimmune/inflammatory syndrome induced by adjuvants: a review

The autoimmune/inflammatory syndrome induced by adjuvants (ASIA) includes several autoimmune conditions and phenomena that occur after exposure to substances with adjuvant activity. The spectrum of the disease is heterogeneous with respect to the clinical presentation as well as the severity of the clinical manifestations. Different substances and medical devices with adjuvant activity are currently known, such as vaccines, oils, silicones, mineral salts, lipopolysaccharides, peptidoglycans, among others. These adjuvants are immunological molecules that function through potentiation of antigen-specific immune responses. Thus, the etiopathogenesis of ASIA syndrome involves a multifactorial interaction between environmental factors and genetic predisposition, and secondary activation of the adaptive and innate arms of the immune system through various mechanisms. Although in some reported cases the ASIA syndrome improves considerably when removing the implants, there are no conclusive results for the clinical benefit of removing the implants, so it is necessary to carry out further basic, clinical and surgical investigations in order to determine the best therapeutic decision

Escoliosis experimental por lesión vascular metamérica a nivel lumbar

Se ha realizado un estudio experimental en 25 híbridos de conejo californiano con conejo blanco gigante neozelandés de 37 ± 3 días, lesionando la vascularización metamé- rica que irriga las vértebras lumbares con el propósito de alterar indirectamente el desarrollo de los cartílagos neurocentrales (CNC). La lesión vascular se produjo por la destrucción unilateral a dos o tres niveles de los vasos metaméricos de las vértebras L3 a L5. Las columnas vertebrales fueron disecadas, realizándose estudios radiológicos, macroscópicos e histológicos. Se obtuvieron curvas escolióticas (13 ±4°) de convexidad hacia el lado contrario al intervenido, con rotación de los cuerpos vertebrales (12 ± 5o ) hacia la concavidad de la curva, y rectificación de la cifosis lumbar fisiológica de los conejos (5 ±7°). El ascpecto macroscópico de las curvas era similar al que se observa en la escoliosis idiopática humana. Estos hallazgos apoyan la idea de que una alteración del desarrollo del CNC por déficit vascular, de forma unilateral, es capaz de inducir la aparición de una escoliosis.We have damaged the vascular supply to the right neurocentral cartilage (NCC) to 25 growing rabbits, in order to induce scoliosis. The employed technique was the section of the right metameric artery and vein at two or three levels in the lumbar region (L3 to L5). The spine was studied histologically macroscopically and radiologically. We got slight curves (13 ±4°) with the convexity towards the opposite side to the operated zone, and with rotation (12 ±5°) and lordosis (5 ± 7°). These lesions are similar to human idiopathic scoliosis and may be explained because of the NCC's physiological properties. Those findings support the idea that any mechanic, metabolic or endocrine alteration that cause damage to the NCC or to its vascularization, unilaterally, will induced a scoliosis development

Evaluation of the nutritional quality of Chaetoceros muelleri Schütt (Chaetocerotales: Chaetocerotaceae) and Isochrysis sp. (Isochrysidales: isochrysidaceae) grown outdoors for the larval development of Litopenaeus vannamei (Boone, 1931) (Decapoda: Penaeidae)

The biomass, proximal composition and fatty acid profile of Isochrysis sp., Chaetoceros muelleri and their mixture, grown under greenhouse conditions, were evaluated. The nutritional value of both species supplied as the monoalgal (Chaetoceros muelleri: Diet I, and Isochrysis sp. Diet II) and mixed diet (Diet III) for larval Litopenaeus vannamei was also assessed on the basis of the development and biochemical composition of the larvae. The highest protein levels were obtained in Diets I and II (40% and 35%, respectively). No significant differences in larval survival were found among the diets; however, larvae fed on Diet II had the lowest mean larval length

Breast reconstruction: a review

Surgeons in the late 19th - 20th century performed radical mastectomies as the only possible treatment for breast cancers. Since then, the medical-surgical/scientific community has been constantly encouraged to develop and study different less invasive alternatives in breast reconstruction. Over time, locoregional perforator flap options have served as practical alternatives to implant-based reconstruction and abdominal flaps, especially in the setting of patients who have received radiation therapy or have a history of failed reconstruction, as they effectively fill the missing volume and respect the musculature of the donor site. Breast reconstruction using strategies with one of the different locoregional flaps can preserve the musculature and innervation of the post-mastectomy site, which manages to reduce possible adverse events. In addition to evaluating the anatomical characteristics of the defect and affected quadrant, it is essential to assess the patient's body constitution and the skills of the surgical team as well as microsurgery training when designing a reconstructive plan. Different research protocols should be developed in the study and development of new medical-surgical therapeutic alternatives; we suggest joint development with tissue engineering

Patrones de abundancia de la macrofauna asociada a macroalgas marinas a largo de la Península Ibérica

macroalgae were studied on a spatial scale along the Iberian Peninsula. Nineteen stations and four dominant algae were selected (intertidal zone: Corallina elongata and Asparagopsis armata; subtidal zone: Stypocaulon scoparium and Cladostephus spongiosus). Five environmental factors were also considered (seawater temperature, conductivity, dissolved oxygen, turbidity and pH). The Atlantic coast was characterized by lower temperature and conductivity as well as higher values of oxygen and turbidity than the Mediterranean coast. A total of 106274 macrofaunal specimens were sorted and examined (68% arthropods, 27% molluscs, 4% annelids and 1% echinoderms). Crustaceans were the dominant group in all the macroalgae (ca. 80% in C. elongata and A. armata, ca. 50% in S. scoparium and C. spongiosus) followed by molluscs, which were more abundant in the subtidal algae (ca. 40%) than in intertidal ones (ca.10%). Abundance patterns of macrofauna along the Iberian Peninsula were similar in the four studied algae. Most of crustaceans belonged to the order Amphipoda, which showed high densities (>1000 ind/1000 ml algae) along the whole Peninsula; isopods showed the highest abundances in the Atlantic, while tanaids, cumaceans and decapods were more abundant in the Mediterranean. Among molluscs, gasteropods showed highest abundances along the Atlantic coasts, whereas bivalves showed higher densities along the MediterraneanSe llevó a cabo un estudio espacial de los patrones de abundancia y distribución de la macrofauna asociada a macroalgas a lo largo de la Península Ibérica. Se seleccionaron 19 estaciones y 4 algas dominantes (zona intermareal: Corallina elongata y Asparagopsis armata; zona submareal: Stypocaulon scoparium y Cladostephus spongiosus). Se consideraron también cinco variables ambientales (temperatura del agua, conductividad, oxígeno disuelto, turbidez y pH). La costa atlántica se caracterizó por valores más bajos de temperatura y conductividad, y más altos de oxígeno y turbidez. Se examinaron 106274 individuos de la macrofauna (68% artrópodos, 27% moluscos, 4% anélidos y 1% equinodermos). Los crustáceos fueron dominantes en todas las macroalgas (alrededor del 80% en C. elongata y A. armata, y en torno al 50% en S. scoparium y C. spongiosus), seguidos por los moluscos, que fueron más abundantes en el submareal (40%) que en el intermareal (10%). Los patrones de abundancia de la macrofauna a lo largo de la Península Ibérica fueron similares en las cuatro algas estudiadas. La mayoría de los crustáceos pertenecieron al orden Amphipoda, que mostró densidades muy altas (>1000 ind/1000 ml alga) en toda la Península; los isópodos mostraron las mayores densidades en el Atlántico, mientras que los tanaidáceos, cumáceos y decápodos fueron más abundantes en el Mediterráneo. Entre los moluscos, los gasterópodos mostraron abundancias mayores en el Atlántico, mientras que los bivalvos dominaron en el Mediterráneo. Teniendo en cuenta que todas las estaciones seleccionadas no tenían influencia antrópica importante, los patrones de abundancia obtenidos podrían explicarse en base a diferencias naturales en la temperatura del agua, oxígeno, conductividad y turbidez, existiendo un gradiente transicional entre taxones de aguas más cálidas (del norte de Africa y del Mediterráneo) y taxones de aguas más frías (del Mar del Norte y el Ártico)

Highly Active and Stable Ni/La-Doped Ceria Material for Catalytic CO2Reduction by Reverse Water-Gas Shift Reaction

[EN] The design of an active, effective, and economically viable catalyst for CO2 conversion into value-added products is crucial in the fight against global warming and energy demand. We have developed very efficient catalysts for reverse water-gas shift (rWGS) reaction. Specific conditions of the synthesis by combustion allow the obtention of macroporous materials based on nanosized Ni particles supported on a mixed oxide of high purity and crystallinity. Here, we show that Ni/La-doped CeO2 catalysts─with the "right"Ni and La proportions─have an unprecedented catalytic performance per unit mass of catalyst for the rWGS reaction as the first step toward CO2 valorization. Correlations between physicochemical properties and catalytic activity, obtained using a combination of different techniques such as X-ray and neutron powder diffraction, Raman spectroscopy, in situ near ambient pressure X-ray photoelectron spectroscopy, electron microscopy, and catalytic testing, point out to optimum values for the Ni loading and the La proportion. Density functional theory calculations of elementary steps of the reaction on model Ni/ceria catalysts aid toward the microscopic understanding of the nature of the active sites. This finding offers a fundamental basis for developing economical catalysts that can be effectively used for CO2 reduction with hydrogen. A catalyst based on Ni0.07/(Ce0.9La0.1Ox)0.93 shows a CO production of 58 × 10-5 molCO·gcat-1·s-1 (700 °C, H2/CO2 = 2; selectivity to CO > 99.5), being stable for 100 h under continuous reaction.We acknowledge the financial support of the Spanish Ministry of Science and Innovation (PID2021-123287OB-I00, PID2021-122477-OB-I00, PID2021-128915NB-I00, and RTI2018-101604-B-I00) and of the CSIC through the i-LINK 2021 program (LINKA20408). Financial support has also been received from AEI-MINECO/FEDER (Nympha Project, PID2019-106315RB-I00), “Comunidad de Madrid” regional government, and the European Structural Funds (FotoArt-CM project, S2018/NMT-4367). Authors also acknowledge financial support from the grant PLEC2021-007906 funded by MCIN/AEI/10.13039/501100011033 and the “European Union NextGenerationEU/PRTR”. We are grateful to ILL (France) for making all facilities available. This project also received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement no. 832121. Computer time provided by the RES (Red Española de Supercomputación) resources at the MareNostrum 4 (BSC, Barcelona) node and the DECI resources at the BEM cluster of the WCSS based in Poland with the support from PRACE aislb is acknowledged

Influence of the Fukushima Dai-ichi nuclear accident on Spanish environmental radioactivity levels

This paper presents measurements of the effect of the atmospheric radioactive release from the Fukushima Dai-ichi nuclear power station at three sites belonging to the Spanish environmental monitoring system. Measured values varied depending on the locations of the sites in Spain and their respective climatic characteristics. 134Cs, 136Cs, 137Cs, 131I, and 132Te activity concentrations in filter samples were studied and associated levels of 131I fallout were estimated from wet and dry deposition. Particulate aerosol activity concentrations ranges, in μBq/m3, were 1.63–3080 (131I), 2.8–690 (137Cs), 1.3–620 (134Cs) and 3.6–330 (132Te), while the associated 131I fallout was roughly estimated to be less than 20 Bq/m2, Gaseous 131I was also detected and the 131I-gaseous/131I-total ratio increased at the three stations from approximately 0.75 at the end of March to 0.85–0.9 during the first few days of April. Finally, the presence of 131I in some crucial parts of the food chain was also studied. 131I was detected in samples from goat's and cow's milk (maximum levels of 1.11 Bq/L) and in broadleaf plants (maximum level 1.42 Bq/kg).The authors gratefully acknowledge financial support from the Spanish Nuclear Security Council (Consejo de Seguridad Nuclear) within the framework of the Environmental Radiological Surveillance Program which operates in Spain under its control and responsibility.Peer reviewe