Search

Keggin H3PW12O40 (PW12) and Wells-Dawson H6P2W18O60 (P2W18) heteropolyacids (HPAs) are photo(catalysts) for various acid-promoted and redox catalytic reactions. Their activity increases if they are deposited on certain supports as metal oxides or carbon materials. Although the surface area and acid-base interactions of the HPAs with supports are considered as key factors for the performance of the binary material, the role of the local structure changes in the HPAs upon their immobilization on solids must be also of primary importance, directly affecting both acidity and photoredox properties. Here, the (photo)catalytic performance of Keggin and Wells-Dawson heteropolytungstates supported on boron nitride (BN) and two types of carbon nitride (C3N4) in the gas-solid 2-propanol dehydration to propene has been studied. Apart from characterizing the materials by a set of conventional laboratory-scale structural and physical-chemical techniques, an insight into the variations of the local structure of supported HPAs is provided by means of X-ray absorption spectroscopy (XAS), and their influence on the supported HPAs (photo)catalytic activity is discussed. The irradiation with UV light increased the activity of both heteropolytungstates with respect to the catalytic experiments. The apparent activation energy calculated for the photo-assisted process resulted always lower with respect to that obtained for the catalytic one alone. Moreover, the materials that showed the highest apparent turnover frequency (TOF) were those in which the HPAs were impregnated on graphitic C3N4 or on BN and, in particular, the highest TOF values were observed at the highest temperature for the PW12/BN and P2W18/BN samples. Interestingly, the highest activity of HPAs supported on BN seems to be due to the stabilization of the W octahedral coordination, according to the XAS data., LFL is grateful to progetto di Ricerca ARS01_00637 Energie per l’Ambiente-TARANTO (PNR 2015-2020) for financial support. IK acknowledges support by Spanish MINECO (MAT2016-78155-C2-1-R), Gobierno del Principado de Asturias (GRUPIN-ID2018-170) and the Alexander von Humboldt Foundation through the Humboldt Research Fellowship. S.V.-R. and J.I.P. acknowledge financial support from the Spanish Ministerio de Ciencia, Innovación y Universidades (MCIU), the Spanish Agencia Estatal de Investigación and European Regional Development Fund (ERDF) through project RTI2018-100832B-I00, and partial funding by Plan de Ciencia, Tecnología e Innovación (PCTI) 2013-2017 del Principado de Asturias and the ERDF (project IDI/2018/000233). A.S acknowledges financial support from the MCIU through the projects MAT2017-86540-C4-1-R and RTI2018-095303-A-C52 and from the Comunidad de Madrid for an “Atracción de Talento Investigador” contract (No. 2017t2/IND5395). The European Synchrotron (ESRF), MCIU and Consejo Superior de Investigaciones Científicas (CSIC) are also acknowledged for the provision of synchrotron radiation facilities. We also thank the BM25-SpLine staff for the technical support beyond their duties.

Polycyclic Aromatic Hydrocarbons (PAHs) are carbon-based molecules resulting from the union of aromatic rings and related species, which are likely responsible for strong infrared emission features (3.3, 6.2, 7.7, 8.6, 11.3 and 12.7 microns). In this work, using a sample of 50 Seyfert galaxies (DL300-400) as well as neutral species. By subtracting the spectrum of the central source from the total, we compare the PAH emission in the central vs extended region of a small sample of AGN. In contrast to the findings for the central regions of AGN-dominated systems, the PAH ratios measured in the extended regions of both type 1 and type 2 Seyfert galaxies can be explained assuming similar PAH molecular size distribution and ionized fractions of molecules to those seen in central regions of star-forming galaxies (100, Comment: 29 pages, 21 figures, 6 tables, MNRAS, accepted 2021 October 22

A fast, effective and low cost sample preparation method based on miniaturized matrix solid-phase dispersion (micro-MSPD) combined with gas chromatography coupled to tandem triple-quadrupole-mass spectrometry (GC–MS/MS) has been developed for the determination of six phthalate diesters (DMP, DEP, DBP, BzBP, DEHP and DnOP) in mussel samples. The six target compounds have been included in the list of priority pollutants by United States Environmental Protection Agency. The extraction step was optimized on real spiked mussel coming from Galician Rías by means of a factorial design. The final procedure involved the use of 0.45 g of sample, 0.5 g of dispersant agent (Florisil) and 3 mL of organic solvent (ethyl acetate). The optimized method was validated giving satisfactory analytical performance, low detection limits (0.09 to 6.73 ng g−1 dw) and high recoveries (93 and 114%). The validated method was applied to four real mussel samples coming from Galician Rías.

The mechanosynthesis route is a physical top–down strategy to produce different nanomaterials. Here, we report the formation of graphene nanoribbons (GNRs) through this route using carbon bars recovered from discarded alkaline batteries as raw material. The mechanosynthesis time (milling time) is shown to have an influence on different features of the GNRs such as their width and edges features. TEM revealed the presence of GNRs with widths of 15.26, 8.8, and 23.55 nm for the milling times of 6, 12, and 18 h, respectively. Additionally, the carbon bars evolved from poorly shaped GNRs for the shortest milling time (6 h) to well-shaped GNRs of oriented sheets forming for the longest milling time. Besides GNRs, graphene sheets (GNS) of different sizes were also observed. The Raman analysis of the 2D bands identified the GNS signal and confirmed the GNRs nature. ID/IG values of 0.21, 0.32, and 0.40 revealed the degree of disorder for each sample. The in-plane sp2 crystallite sizes (La) of graphite decreased to 91, 60, and 48 nm with increasing peeling time. The RBLM band at 288 cm−1 confirmed the formation of the GNRs. Mechanosynthesis is a complex process and the formation of the GNRs is discussed in terms of a mechanical exfoliation, formation of graphene sheets and its fragmentation to reach GNR-like shapes. It is shown that the synthesis of GNRs through the mechanosynthesis route, besides the use of recycled materials, is an alternative for obtaining self-sustaining materials.

Remote sensing methods enable detection of solar-induced chlorophyll a fluorescence. However, to unleash the full potential of this signal, intensive cross-disciplinary work is required to harmonize biophysical and ecophysiological studies. For decades, the dynamic nature of chlorophyll a fluorescence (ChlaF) has provided insight into the biophysics and ecophysiology of the light reactions of photosynthesis from the subcellular to leaf scales. Recent advances in remote sensing methods enable detection of ChlaF induced by sunlight across a range of larger scales, from using instruments mounted on towers above plant canopies to Earth-orbiting satellites. This signal is referred to as solar-induced fluorescence (SIF) and its application promises to overcome spatial constraints on studies of photosynthesis, opening new research directions and opportunities in ecology, ecophysiology, biogeochemistry, agriculture and forestry. However, to unleash the full potential of SIF, intensive cross-disciplinary work is required to harmonize these new advances with the rich history of biophysical and ecophysiological studies of ChlaF, fostering the development of next-generation plant physiological and Earth-system models. Here, we introduce the scale-dependent link between SIF and photosynthesis, with an emphasis on seven remaining scientific challenges, and present a roadmap to facilitate future collaborative research towards new applications of SIF.

10 pages, 5 figures.-- Under a Creative Commons license., Understanding the ocean carbon sink and its future acidification-derived changes requires accurate and precise measurements with good spatiotemporal coverage. In addition, a deep knowledge of the thermodynamics of the seawater carbonate system is key to interconverting between measured and calculated variables. To gain insights into the remaining inconsistencies in the seawater carbonate system, we assess discrete water column measurements of carbon dioxide fugacity (fCO2), dissolved inorganic carbon (DIC), total alkalinity (TA), and pH measured with unpurified indicators, from hydrographic cruises in the Atlantic, Pacific, and Southern Oceans included in GLODAPv2.2020 (19,013 samples). An agreement of better than ± 3% between fCO2 measured and calculated from DIC and pH is obtained for 94% of the compiled dataset, while when considering fCO2 measured and calculated from DIC and TA, the agreement is better than ± 4% for 88% of the compiled dataset, with a poorer internal consistency for high-CO2 waters. Inspecting all likely sources of uncertainty from measured and calculated variables, we conclude that the seawater carbonate system community needs to (i) further refine the thermodynamic model of the seawater carbonate system, especially K2, including the impact of organic compounds and other acid-base systems on TA; (ii) update the standard operating procedures for the seawater carbonate system measurements following current technological and analytical advances, paying particular attention to the pH methodology that is the one that evolved the most; (iii) encourage measuring discrete water column fCO2 to further check the internal consistency of the seawater carbonate system, especially given the new era of sensor-based seawater measurements; and (iv) develop seawater Certified Reference Materials (CRMs) for fCO2 and pH together with seawater CRMs for TA and DIC over the range of values encountered in the global ocean. Our conclusions also suggest the need for a re-evaluation of the adjustments applied by GLODAPv2 to pH, which were based on DIC and TA consistency checks but not supported by fCO2 and DIC consistency, The research leading to these results was supported through NOAA's Ocean Acidification Program (OAP) via Award #NA17OAR0170332; through NERC via project NE/P021263/1; through the Spanish Research Agency via project PID2019-104279GB-C21/AEI/10.13039/501100011033; and through GAIN via grant IN607A2018/2, With the institutional support of the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000928-S)

The success of a Rhizobium sp. inoculant depends on a product with a high number of live bacteria that can nodulate a leguminous plant. Culture media and oxygen transfer were studied to improve the production of R. phaseoli in chemically defined and undefined media for scale-up from shake flasks to a pneumatic bioreactor. The effects of carbon and phosphate on R. phaseoli growth were evaluated, and the specific volumetric oxygen transfer coefficient (KLa) was determined in shake flasks and scale-up to bioreactors. Six-fold more viable biomass was obtained by increasing the phosphate concentration by 7.5-fold when using glucose. However, this increase was not observed when succinate was used. In the undefined medium, glucose induced a higher production of R. phaseoli in comparison with other carbon sources. The KLa of 6–11 h-1 produced a five-fold growth of biomass in shake-flask cultures. This KLa was used to produce a R. phaseoli-based inoculant in a bioreactor. The formation of nitrogen-fixing nodules was confirmed in bean plants (Phaseolus vulgaris). The improvement of culture media with a suitable oxygen transfer demonstrates that R. phaseoli can be used as an inoculant that exerts beneficial effects on the initial growth of bean plants.

A miniaturized methodology was developed and applied to the determination of fourteen organochlorine pesticides (OCPs) in mussel samples. This approach was based on matrix solid phase dispersion that enabled to perform extraction and clean-up of the sample at the same step. Subsequently, the extracts were readily analyzed by gas chromatography−tandem mass spectrometry. The extraction and clean-up parameters, amounts of sample, drying agent (anhydrous sodium sulfate) and dispersant agent (Florisil) and solvent volume and polarity (mixture) were optimized by using a fractional factorial design 25–1. Four of five factors, namely, sample and Florisil amounts, solvent volume and solvent mixture, were statistically significant for some of OCPs. The analytical performance demonstrated a broad linear range (R2 < 0.998), recoveries around 85% and relative standard deviation below 7%. The methodology was applied to the analysis of three mussel samples coming from Rias of Ferrol and A Coruna in Galicia coast (NW, Spain).

A set of C3N4 samples has been prepared by using melamine, cyanuric acid and barbituric acid as the precursors. The materials were subjected both to physical and chemical characterization and were used as photocatalysts for the selective oxidation of aromatic alcohols in water suspension under UV and visible irradiation. The photoactivity of the materials versus the partial oxidation of four substituted benzyl alcohols was investigated. The type and position of the substituents in the aromatic molecule influenced conversion and selectivity to the corresponding aldehyde. The presence of barbituric and cyanuric acids in the preparation method has changed the graphitic-C3N4 structure, and therefore both the characteristics of the material and the ability of light to activate the surface of the photocatalyst. The most active material prepared in the presence of melamine and cyanuric acid showed a remarkable selectivity towards the aldehyde even under visible irradiation.

espanolLa fritura repetida de alimentos produce termooxidacion y polimerizacion, potencialmente negativas para la salud. Se desconoce como reacciona el sistema gastrointestinal frente a estos compuestos. Las proantocianidinas poseen propiedades antioxidantes e hipolipemiantes. Hipotetizamos que un extracto de algarrobo rico en proantocianidinas (CFE) mejora la defensa del intestino frente a la agresion termooxidativa. Se estudio, en el aceite de girasol, la termooxidacion producida por la fritura repetida de pescado y, en ratas Wistar, el efecto de administrar conjuntamente aceite de fritura y CFE sobre: la digestion de los compuestos termooxidados, la lipemia postprandial, las proteinas implicadas en la absorcion de lipidos, y la actividad y expresion antioxidante y de hemo-oxigenasa-1 en intestino delgado. Doce ratas Wistar, macho, de 200-250 g fueron canuladas durante una semana con la mezcla del aceite termooxidado-CFE o con aceite termooxidado. Se cuantifico la alteracion termooxidativa en el aceite de fritura y en la grasa postprandial del lumen gastrointestinal, la lipemia postprandial, las proteinas NPC1L1, ACAT-2 y MTP, y el estado antioxidante en duodeno, yeyuno e ileon. Se encontraron niveles elevados de compuestos de polimerizacion y trigliceridos oxidados en el aceite de girasol y en la grasa del lumen gastrointestinal. La administracion de aceite de girasol termooxidado-CFE disminuye la digestibilidad del aceite y de los compuestos polimericos/termooxidados, aminora la lipemia postprandial, eleva NPC1L1, ACAT-2 y MTP, y mejora el estado antioxidante intestinal y la excrecion de polimeros fecales. El empleo de CFE reduce la lipemia postprandial y garantiza un estado antioxidante intestinal adecuado frente a lipidos termooxidados. EnglishThe repeated frying of food in sunflower oil produces thermo-oxidation and polymerization, potentially negative for health. The reaction of the gastrointestinal system to these compounds is unknown. Proanthocyanidins have antioxidant and lipid-lowering properties. We hypothesize that a carob-fruit extract rich in proanthocyanidins (CFE) improves the defense of the intestine against thermo-oxidative aggression. In sunflower oil, the thermo-oxidation produced by repeated frying of fish was studied while, in Wistar rats, the effect of jointly administering altered sunflower oil and CFE on: the digestion of thermo-oxidized compounds, postprandial lipaemia, proteins involved in lipid absorption, antioxidant and hemoxygenase-1 activity and expression in the small intestine. Twelve male Wistar rats, 200-250 g were cannulated for one week with the mixture of the thermo-oxidized oil-CFE or the thermo-oxidized oil. Thermo-oxidation was determined in sunflower oil and in the postprandial-fat of the gastrointestinal lumen, postprandial lipaemia, the proteins NPC1L1, ACAT-2 and MTP, and the antioxidant status in the duodenum, jejunum and ileum. High thermo-oxidation and polymerization levels were found on sunflower oil and fat in the gastrointestinal lumen. The administration of thermo-oxidized sunflower oil-CFE decreases the digestibility of the oil and the polymeric/thermo-oxidized compounds, reduces postprandial lipaemia, increases NPC1L1, ACAT-2, and MTP, and improves the intestinal antioxidant status and excretion of fecal polymers. The use of CFE reduces postprandial lipaemia and guarantees an adequate intestinal antioxidant status against thermo-oxidized lipids.

This study reports the differences in the protein composition of salivary pellicles formed under in situ conditions on two Titanium (Ti) surfaces, with different roughness and wettability. Smooth pretreatment Ti surfaces (Ti-PT) with an average roughness (Ra) of 0.45 μm and a water contact angle (WCA) of 92.4°, as well as a more rough sandblasted, large grit, acid-etched treatment Ti surfaces (Ti-SLA) with a Ra of 3.3 μm and WCA of 131.8°, were tested. The salivary pellicles were quantitatively analyzed by bicinchoninic acid assays, and the protein identification was performed by Nano-LC-MS/MS (nano mass spectrometry). Protein levels of 2.5, and 9.1 μg/ml were quantified from the detached salivary pellicle formed on the Ti-PT and Ti-SLA surfaces, respectively. Using Nano-LC-MS/MS, a total of 597 proteins were identified on all the substrates tested; 43 proteins were identified only on the Ti-PT, and 226 proteins were adsorbed solely on the Ti-SLA substrates. The physicochemical characteristics of the Ti implant surfaces modified the amount and the identity of the salivary proteome of the pellicles formed, confirming the high selectivity of the protein pellicle formed on a surface once is exposed in the oral cavity.

During the incubation period, the Ca-to-P weight (mg/mg) ratio in the yolk increases from 0.26 on day 0 to 0.92 on day 17.5 and to 2.9 at hatch. Moreover, the absolute Ca content in the yolk increases by 41%, whereas P content decreases by 87%, from day 0 to the day of hatching. Thus, at hatch and during the first days after hatching, there are high reserves of Ca relative to P in the residual egg yolk, risking hypercalcemia and hypophosphatemia. A growth performance study was conducted to explore the effects of reducing dietary Ca content in the prestarter phase (0–4 D) on BW and bone mineral deposition during the first days after hatch and at market weight (day 37). Four prestarter (0–4 D) diets were formulated to have 0.4, 0.6, 0.8, and 1.0% Ca content. After the prestarter phase, all birds were fed with the same commercial diets based on a 3-phase feeding program (starter, grower, and finisher). Growth performance (BW, ADG, ADFI, and feed conversion ratio [FCR]) was monitored throughout the study, and blood and tibia bone samples were collected on specific days. On day 4, BW and ADG decreased with dietary Ca contents higher than 0.6% (P 0.10). For the overall study (0–37 D), there were no differences in ADG and ADFI, but the FCR decreased with lower Ca contents (P 0.10). In conclusion, during the prestarter phase, BW increased with dietary Ca contents lower than 0.6%, most likely improving Ca–P balance; bone mineral deposition was reduced in this period. On feeding with a diet containing higher Ca content, bone mineral content was rapidly recovered.

In this work, a simple microwave method was utilized to prepare ZnO sheet linked with Fe3O4@rGO core–shell and of Ag2CO3 through formation of the quadri-photocatalytic with high activity. The microstructure, morphology, spectroscopic, and magnetic characteristics of the prepared samples were assessed using XRD, SEM, PL, TEM, FT-IR, DLS, and VSM analysis. The photocatalytic activity of the material was evaluated for photodegradation of methylene blue dye under the UV and visible light with home-made photoreactor. The response surface method in a Box–Behnken design was utilized to design the experiments. The parameters affecting the efficiency of the degradation including, pH (5–9), photocatalyst dose (50–150mg), contact time (30–90min), and radiation power (30–60W) were studied and optimized. The optimum parameters were found to the initial concentration of 10ppm, after a reaction time of 63.65min, the amount of the catalyst of 150mg, the pH of 8.99, and 94.99% of degradation (in the radiation power of 45W).

The effects of formulating broiler diets that contain sources of either rapidly or slowly digestible protein and 2 different dietary fiber sources on growth performance were studied in broilers chickens from 0 to 36 d of age. A total of 1,920 one-day-old, male Ross 708 broiler chickens were randomly allocated and housed in 48 floor pens (40 birds/pen) to one of 4 dietary treatments. Birds were allotted according to a completely randomized block design using a factorial arrangement of treatments with 2 protein digestion rates (rapidly or slowly) and 2 dietary fiber sources [3% oat hulls (OH) or 3% sugar beet pulp (SBP)] from 0 to 36 d of age. All diets were formulated to be isocaloric and isonitrogenous. The pen was the experimental unit for all variables studied (12 replicates/treatment). Data were analyzed using the MIXED procedure of SAS, and the model included the main effects of the protein digestion rate, dietary fiber source, and their interaction. There were 3 experimental feeding phases; starter (from day 0-14), grower (from day 14-28), and finisher (from day 28-36). Results indicated that broilers fed diets containing sources that supplied more rapidly digestible protein had 4% greater (P < 0.01) ADG and improved (P < 0.01) the feed conversion ratio (FCR) by 5% throughout the experiment, most notably after the starter phase. Diets containing 3% OH increased (P < 0.05) the ADFI and ADG (P < 0.05) in the starter phase compared with broilers fed diets containing 3% SBP, without affecting the FCR. The ADG and FCR of broilers fed diets containing sources of slowly digestible protein were improved (P < 0.05) to the level of broilers fed rapidly digestible protein containing diets with the addition of 3% OH. It is concluded that broiler diets should be formulated to contain a high concentration of ingredients that supply rapidly digestible protein, but if this is cost-prohibitive, then 3% OH could be used to increase the ADFI and ADG and potentially protein digestion rates to reduce the FCR.

The purpose of this study was to develop a biodegradable thermoplastic polymer based on starch and polylactic acid (PLA) blends with mechanical properties adequate for a wide range of applications. A thermoplastic starch (TPS) was formulated using native corn starch, glycerol as a plasticizer ranging from 30 to 50% (w/w) and citric acid (1.0%, w/w) as a crosslinker. The TPS was mixed with polylactic acid (PLA) [0-50%, w/w]. The material was prepared by extrusion using a single screw extruder. The variables for the experiment design were PLA concentration, extrusion temperature, glycerol concentration, and velocity of the screw. Samples before and after extrusion were characterized by Scanning Electron Microscopy (SEM), Differential Scanning Calorimetry (DCS), Fourier Transform Infrared Spectroscopy (FTIR) and X-Ray Diffraction. We evaluated the mechanical Young’s modulus, tensile strength, and elongation at break. All treatments were performed according to the experiment design. The results of the characterization of the material were analyzed using the response surface methodology (RSM). The RSM revealed the optimum PLA concentration, extrusion temperature, and screw velocity that would produce a corn starch-PLA biodegradable plastic with mechanical properties closer to those of the petroleum-derived plastics.

In this research, effects of macronutrient deficiency (N, P, K, Ca, and Mg) on the production, physicochemical characteristics, minerals, phenolic compounds, and antioxidant capacity of fig fruits (Ficus carica L.) were evaluated using the missing element technique in a controlled hydroponic system under greenhouse conditions. N-deficient plants had no fruit production, while fruits with absence of P, K, and Ca were the most affected in terms of size, weight, and physicochemical characteristics. On the other hand, the concentration of minerals was significantly different (p

Summary: Heat stress is a major problem in the poultry industry, especially during summer months and when birds are raised under high-density conditions. Previous studies have reported that vitamin C or electrolyte supplementation could palliate the effects of heat stress in broiler chickens. The present study evaluated the effect of a mineral and vitamin mix (AHS) added to drinking water on the performance of broiler chickens. In total, 1,824 one-day-old birds were randomly allocated to 48 pens. Maximum animal density was 26.5 kg/m2. The control group received no additive; AHS-1 and -2 groups received the AHS mix at a concentration of 1 and 2 kg/1,000 L in drinking water, respectively; and the Vit-C group received vitamin C in drinking water at 200 g/1,000 L. All birds were fed the same diets based on a 3-phase feeding program; feed and water were given on ad libitum basis. To mimic heat stress conditions, temperature in the barn was raised to 35 C from 08:00 to 14:00 h each day. For the overall growing period (0 to 35 D), adding AHS to drinking water increased final BW, ADG, and ADFI linearly (PLinear 0.10). No significant effect on mortality were found (8.77%; P > 0.10). Relative to control, all the treatments tested reduced (P < 0.05) corticosterone concentration in blood serum. In conclusion, the combined use of supplementary levels of minerals and vitamins could alleviate the effects of heat stress on broilers chickens.

Au nanoparticles supported on CeO2 have been prepared and investigated as photocatalysts for the photocatalytic selective oxidation of benzyl alcohol and 4-methoxybenzyl alcohol to the correspondent benzaldehydes, in aqueous suspensions and room conditions under UV, visible and natural solar light irradiation. Au nanoparticles have been supported by impregnation (1 and 3 wt.%) on two types of CeO2 (i.e., a commercial one and a home prepared oxide obtained in the presence of NaOH as precipitation agent). The Au impregnated samples showed strong visible radiation absorption at 565–570 nm associated to localized surface plasmon resonance (LSPR). The bare CeO2 samples are activated by UV light and resulted virtually inactive under visible irradiation, whereas the presence of Au improved both the conversion of the alcohols and the selectivity of the reaction towards the aldehyde, giving rise to good results, particularly under visible and natural solar light irradiation. The activity of the materials increased by increasing the Au content.

The aim of this study was the quantification of Sphingosine-1-phosphate (S1P) in periodontal pockets of patients with periodontitis. This is an observational, descriptive, case-control study. Thirty subjects were selected: 15 controls and 15 cases. A periodontal study was conducted following the parameters of AAP 2017 for the diagnosis of periodontal diseases. A sample of saliva and gingival crevicular fluid was obtained from each subject and then analyzed with the Human S1P Elisa kit (MyBioSource #MBS2516132) accordingly to the manufacturer's instructions, in order to verify the presence of S1P and quantify it´s concentration when founded. Results showed a significant difference (p=0.05) between cases and controls. In the case of saliva samples, the concentration of S1P was higher than the ones found in the control group (72.94 ng/mL and 45.12 ng/mL). For GCF, a higher amount of S1P was found in patients with POD (20.09 ng/mL and 15.20 ng/mL). This work raises a possible route of bone metabolism, inflammatory process, and identification of periodontitis through oral quantification of S1P, however, future studies are needed. Resumen El propósito de este estudio fue la cuantificación de Esfingosina-1-Fosfato (S1P) en las bolsas periodontales de pacientes con periodontitis. Estudio observacional, descriptivo de casos y controles. 30 sujetos fueron seleccionados de los cuales 15 controles y 15 casos. Se realizó un estudio periodontal completo siguiendo los parámetros establecidos por la AAP en 2017 para el diagnóstico de las enfermedades periodontales. Se tomaron muestras de saliva y de líquido crevicular gingival de cada sujeto estudiado y se analizaron con el ELISA kit humano para S1P (MyBiosource #MBS2516132) y de acuerdo con las instrucciones del fabricante, se realizó para cuantificar la presencia d S1P en las muestras estudiadas. Los resultados mostraron diferencia significativa (p=0.05) entre casos y controles. En el caso de las muestras de saliva, la concentración de S1P en controles fue mayor (72.94 ng/mL y 45.12 ng/mL). Para Líquido crevicular gingival, se encontró mayor cantidad de S1P en los pacientes con periodontitis (20.09 ng/mL y 15.20 ng/mL). Este estudio plantea una posible ruta de metabolismo óseo, proceso inflamatorio e identificación de la Periodontitis a través de la cuantificación oral de S1P, sin embargo se necesitan estudios futuros.

Resumen: Antecedentes y objetivo: La actualización de las series estándar de pruebas epicutáneas debe basarse en datos objetivos de frecuencia de sensibilización de los alérgenos que componen cada batería. La última renovación de la batería estándar española se realizó en 2016 y de la europea en 2019, quedando pendiente valorar la inclusión de alérgenos emergentes. Material y método: Desarrollamos un estudio observacional, prospectivo y multicéntrico de los pacientes consecutivos del registro del Grupo Español de Investigación en Dermatitis y Alergia Cutánea sometidos a pruebas epicutáneas con hidroperóxido de linalool, hidroperóxido de limoneno, 2-hidroxi-etil-metacrilato, benzisotiazolinona, octilisotiazolinona, mezcla textil, metabisulfito sódico, propóleo, bronopol, mezcla de compuestas II, diazolidinil urea, imidazolidinil urea, decil glucósido y lauril glucósido, durante los años 2019 y 2020. Resultados: Se analizó una muestra de 4.654 pacientes estudiados con diazolidinil urea, imidazolidinil urea y bronopol, y de 1.890 pacientes con el resto de los alérgenos. El índice MOAHLFA fue: M 30%, O 18%, A 15%, H 29%, L 6,5%, F 23%, A 68%. Siete alérgenos mostraron una frecuencia de sensibilización mayor del 1%: hidroperóxido de linalool, 2-hidroxi-etil-metacrilato, benzisotiazolinona, hidroperóxido de limoneno, mezcla textil, metabisulfito sódico y propóleo. Tres alérgenos mostraron una frecuencia de relevancia presente superior al 1%: hidroperóxido de linalool, 2-hidroxi-etil-metacrilato e hidroperóxido de limoneno; para benzisotiazolinona y mezcla textil, esta frecuencia fue de entre el 0,9 y el 1%. Conclusiones: Nuestros resultados indican que debería valorarse la inclusión de siete nuevos alérgenos en la batería estándar española. Estos resultados podrían contribuir a la próxima actualización de la batería basal europea. Abstract: Background: Standard patch test series must be updated using objective data on allergen sensitization. The Spanish standard series was last updated in 2016 and the European series in 2019, and the inclusion of several emerging allergens needs to be evaluated. Material and methods: We conducted a prospective, observational, multicenter study of consecutive patients from the registry of the Spanish Contact Dermatitis and Skin Allergy Research Group (GEIDAC) who were patch tested in 2019 and 2020 with linalool hydroperoxide, limonene hydroperoxide, 2-hydroxyethyl-methacrylate, benzisothiazolinone, octylisothiazolinone, textile dye mix (TDM), sodium metabisulfite, propolis, bronopol, Compositae mix II, diazolidinyl urea, imidazolidinyl urea, decyl glucoside, and lauryl glucoside. Results: We analyzed data for 4654 patients tested with diazolidinyl urea, imidazolidinyl urea, and bronopol, and 1890 tested with the other allergens. The values for the MOAHLFA index components were 30% for male, 18% for occupational dermatitis, 15% for atopic dermatitis, 29% for hand, 6.5% for leg, 23% for face, and 68% for age > 40 years. Sensitization rates above 1% were observed for 7 allergens: linalool hydroperoxide, 2-hydroxyethyl-methacrylate, benzisothiazolinone, limonene hydroperoxide, TDM, sodium metabisulfite, and propolis. Three allergens had a current relevance rate of over 1%: linalool hydroperoxide, 2-hydroxyethyl-methacrylat, and limonene hydroperoxide. Benzisothiazolinone and TDM had a relevance rate of between 0.9% and 1%. Conclusions: Our results indicate that 7 new allergens should be considered when extending the Spanish standard patch test series. The data from our series could be helpful for guiding the next extension of the European baseline series.

Magnetic separation of the solid photocatalyst from the reacting suspension has received great interest in recent research because it offers a suitable way for removing and recycling the heterogeneous photocatalytic material particles preventing the agglomeration and sedimentation during and after their use. The use of iron oxides such as heterogeneous photocatalysts is an appropriate choice to obtain a suitable photocatalyst easily separable from the fluid. This chapter presents a detailed investigation of iron oxide-based magnetic photocatalysts (IOMPs). We will discuss the required conditions for the synthesis of these photocatalysts, followed by their applications for the removal of organic pollutants. The combination of iron oxides (or other metal-FeO cores) with polymers, metal oxides, and carbonic materials is also elucidated. The chapter shows the advancements toward the synthesis of stable IOMPs, their physical–chemical features, appearance, recyclability, and photocatalytic efficacy.

The most common nosocomial fungal infections are caused by several species of Candida, of which Candida glabrata is the second most frequently isolated species from bloodstream infections. C. glabrata displays relatively high minimal inhibitory concentration values (MIC) to the antifungal fluconazole and is associated with high mortality rates. To decrease mortality rates, the appropriate treatment must be administered promptly. C. glabrata contains in its genome several non-identical copies of species-specific sequences. We designed three pairs of C. glabrata-specific primers for endpoint PCR amplification that align to these species-specific sequences and amplify the different copies in the genome. Using these primers, we developed a fast, sensitive, inexpensive, and highly specific PCR-based method to positively detect C. glabrata DNA in a concentration-dependent manner from mixes of purified genomic DNA of several Candida species, as well as from hemocultures and urine clinical samples. This tool can be used for positive identification of C. glabrata in the clinic. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s42770-021-00584-2.

Broiler chickens have an extreme physiology (rapid growth rates) that challenges the correct bone mineralization, being an interesting animal model for studying the development of bone pathologies. This work studies in detail how the mineralization, chemistry, and structural organization of tibiae bone in broiler chickens change with age during the first 5 wk (37 D) from hatching until acquiring the final weight for slaughter. During the early growth phase (first 2 wk), the rapid addition of bone tissue does not allow for bone organic matrix to fully mineralize and mature, and seems to be a critical period for bone development at which bone mineralization cannot keep pace with the rapid growth of bones. The low degree of bone mineralization and large porosity of cortical bone at this period might be responsible of leg deformation and/or other skeletal abnormalities commonly observed in these birds. Later, cortical bone porosity gradually decreases and the cortical bone became fully mineralized (65%) at 37 D of age. At the same time, bone mineral acquires the composition of mature bone tissue (decreased amount of carbonate, higher crystallinity, Ca/P = 1.68). However, the mineral part was still poorly organized even at 37 D. The oriented fraction was about 0.45 which means that more than half of apatite crystals within the mineral are randomly oriented. Mineral organization (crystal orientation) had an important contribution to bone-breaking strength. Nevertheless, locally determined (at tibia mid-shaft) bone properties (i.e., cortical thickness, crystal orientation) has only a moderate correlation (R2 = 0.33) with bone breaking strength probably due to large and highly heterogeneous porosity of bone that acts as structural defects. On the other hand, the total amount of mineral (a global property) measured by total ash content was the best predictor for breaking strength (R2 = 0.49). Knowledge acquired in this study could help in designing strategies to improve bone quality and reduce the incidence of skeletal problems in broiler chickens that have important welfare and economic implications.

An innovative protocol to electrodeposit ZnS:nano-MoS2 composite coatings with enhanced tribological properties is reported. The mechanisms involved in the deposition process are analyzed by cyclic voltammetry. The morphology and composition of the ZnS:nano-MoS2 composite coatings are characterized. The tribological performance of the coatings is studied through pin-on-disk tests. The chemical composition of the wear tracks are characterized in order to gain further insight into the mechanisms behind of the self-lubricating ability of the ZnS:nano-MoS2 coatings. Key role for not only MoS2 –i.e. lubricating ability-, but also ZnS as a relatively soft matrix –i.e. providing supplementary sulphur to the Mo S tribofilm formation- is suggested. The ZnS:nano-MoS2 composite coatings deposited from 10 g/L MoS2 nanoparticle electrolytes exhibit decreased and stable pin-on-disk friction coefficient of approximately 0.1 under 2 N of normal load.

The developmental period in utero is a critical window for environmental exposure. Epigenetic fetal programming via DNA methylation is a pathway through which metal exposure influences the risk of developing diseases later in life. Genetic damage repair can be modified by alterations in DNA methylation, which, in turn, may modulate gene expression due to metal exposure. We investigated the impact of prenatal metal exposure on global and gene-specific DNA methylation and mRNA expression in 181 umbilical cord blood samples from newborns in Mexico City. Global (LINE1) and promoter methylation of DNA-repair (OGG1 and PARP1) and antioxidant (Nrf2) genes was evaluated by pyrosequencing. Prenatal metal exposure (As, Cu, Hg, Mn, Mo, Pb, Se, and Zn) was determined by ICP-MS analysis of maternal urine samples. Multiple regression analyses revealed that DNA methylation of LINE1, Nrf2, OGG1, and PARP1 was associated with potentially toxic (As, Hg, Mn, Mo, and Pb) and essential (Cu, Se, and Zn) elements, and with their interactions. We also evaluated the association between gene expression (mRNA levels quantified by p-PCR) and DNA methylation. An increase in OGG1 methylation at all sites and at CpG2, CpG3, and CpG4 sites was associated with reduced mRNA levels; likewise, methylation at the CpG5, CpG8, and CpG11 sites of PARP1 was associated with reduced mRNA expression. In contrast, methylation at the PARP1 CpG7 site was positively associated with its mRNA levels. No associations between Nrf2 expression and CpG site methylation were observed. Our data suggest that DNA methylation can be influenced by prenatal metal exposure, which may contribute to alterations in the expression of repair genes, and therefore, result in a lower capacity for DNA damage repair in newborns.

This paper reports a rapid, economic and efficient process to prepare calcium phosphate nanoparticles (nFC), also known as hydroxyapatite. The objective of this study was to synthesize, characterize and determine the effect of the agitation type on the production and morphology of nFC. The synthesis was carried out by wet chemical precipitation, with mechanical and magnetic agitation. TEM microscopy indicates that mechanical agitation produced ~ 33% particles with diameter between 15-20 nm, while magnetic stirring formed 29% (12.12% less). The sizes range obtained for both agitations types was 10 to 45 nm, with the predominant size being 15 to 20 nm. The FTIR spectrometry analysis revealed that the nFC obtained are analogous to those reported in the literature. Ζeta potential values of -20 mV to -14 mV were obtained for mechanical and magnetic agitation respectively, suggesting that nFC synthesized by mechanical agitation is more stable in solution. The results obtained reveal that mechanical agitation improves the characteristics of the nanocomposite, so this technique should be validated. We consider that the process reported here could be scalable to produce nFC, which has commercial potential as a nanofertilizer for the agricultural sector

The application of non-destructive techniques for the evaluation of internal damage in composite materials is a challenge due to their complexity. The aim of this study is to analyse the ability of ultrasonic technique to identify and evaluate manufacturing defects and internal damage in composite laminates. Artificial object inclusions of different shapes, sizes and materials were embedded in carbon fibre reinforced epoxy (CFRP) laminates. Comprehensive investigation of non-destructive evaluation using phased array ultrasonic testing to trace and characterize the embedded defects is presented. Phased array ultrasonic technique was able to precisely locate most of the artificial inclusion in the composite laminates. Nerveless, the shape and size of the inclusions were not accurately determined due to the high signal attenuation and distortion characteristics of the carbon fibre epoxy composite. Furthermore, a major concern affecting the efficient use of composite laminates is their vulnerability to low velocity impact damage. The dynamic behaviour of composite laminates is very complex as there are many concurrent phenomena during composite laminate failure under impact loading. Thus, the practicality of the previous results is demonstrated by the evaluation of impacted carbon fibre reinforced epoxy laminates using ultrasonic testing. The influence of laminate thickness and impact energy on impact damage is also investigated. The performance of phased array ultrasonic testing for the inspection of composite laminates with barely visible impact damage is evaluated. In addition, fibre-reinforced thermoplastic composites are becoming more significant in industrial applications due to their excellent mechanical performance and potential recycling. In this study, impact damage in 3D printed continuous glass fibre reinforced thermoplastic laminates is also analysed. Phased array ultrasonic testing is performed and the amount of damage is quantified in terms of delaminated area.

International audience; Supercritical carbon dioxide has been used to develop two methods for the impregnation of porous silica beads with a natural antioxidant, quercetin. These methods involved batch and semi-continuous supercritical impregnations. The first experiments performed in batch mode helped to understand the influence of pressure, temperature, duration, and the presence of a co-solvent on the impregnation efficiency. A co-solvent was added due to the low solubility of quercetin in supercritical CO2 under the operating conditions studied. In the range of temperatures and pressures studied, the best operating conditions, i.e., those that led to the highest quantity of quercetin impregnated (300 mu g of quercetin per g of silica), were 10 MPa and 323 K with ethanol as co-solvent for 2 h. These operating conditions, highlighted through the batch mode experiments, were subsequently applied to the semi-continuous process. This approach provided an impregnation ratio of 240 mu g of quercetin per g of silica.

Chronic kidney disease is one of the main comorbidities affecting liver transplant recipients. Most of those patients have some degree of acute or chronic kidney dysfunction at the time of transplantation, moreover they can also develop de novo chronic kidney disease once transplanted. An important increase in the incidence of chronic kidney disease in the «MELD era» has been observed. This phenomenon has partially been attributed to the weight that kidney function carries for organ allocation. In addition, the generalized use of calcineurin inhibitors has also been a contributing factor. It is of the utmost importance for us to be familiar with the current methods for evaluating kidney function before and after a liver transplantation. The two main biomarkers available today for that purpose are serum creatinine and cystatin C. Several equations have been derived from those biomarkers and have been tested in that context with mixed results, due to their biologic variability and the lack of standardization in their measurement. The gold standard continues to be the direct determination of the glomerular filtration rate through different methods, however that is only done for research purposes. It is also essential to know the current classification of acute kidney injury and chronic kidney disease in order to make early diagnosis. The present review focuses on the recognition, diagnosis, and classification of chronic kidney disease and acute kidney injury in liver transplantation recipients. Resumen: La enfermedad renal crónica (ERC) es una de las principales comorbilidades que afectan a los pacientes receptores de trasplante hepático. Muchos de ellos son trasplantados con cierto grado de disfunción renal aguda o crónica, sin embargo, también pueden desarrollar ERC de novo una vez trasplantados. Se ha observado un incremento importante de la incidencia de ERC en la «era MELD», en parte se ha atribuido este fenómeno al peso que tiene la función renal para la asignación de órganos. Por otro lado, el uso generalizado de inhibidores de calcineurina también ha contribuido a este fenómeno. Es de suma importancia familiarizarnos con los métodos actuales para evaluar la función renal antes y después de un trasplante hepático. Los 2 principales biomarcadores disponibles hoy en día para este fin son la creatinina sérica y la cistatina C. Existen varias ecuaciones derivadas de estos biomarcadores que han sido probadas en este contexto, obteniéndose resultados mixtos debido a su variabilidad biológica y a la falta de estandarización en su determinación. El estándar de oro continúa siendo la medición directa de la tasa de filtrado glomerular por diversos métodos, sin embargo, esto solo se realiza con fines de investigación. También es importante conocer la clasificación actual de la lesión renal aguda y de la ERC con el fin de poder realizar un diagnóstico temprano. Esta revisión se centra en el reconocimiento, diagnóstico y clasificación de la ERC y la lesión renal aguda en pacientes receptores de trasplante hepático. Keywords: Liver transplantation, Chronic kidney disease, Glomerular filtration rate, Acute kidney injury, Palabras clave: Trasplante hepático, Enfermedad renal crónica, Tasa de filtrado glomerular, Lesión renal aguda

Recientemente se ha reportado el potencial de los nanofertilizantespara incrementar rendimientos de los cultivos. Las nanopartículas de hidroxiapatita(nHAp) se aplican como fertilizantes a las plantas por su alto contenido en Py Ca (Ca10(PO4)6(OH)2), pero hay escasa información al respecto. El objetivodel trabajo fue producir nHAp sintético, caracterizarlo y evaluar su efecto comonutriente en el desarrollo de plántulas de rábano (Raphanus sativus) variedadChampion. La síntesis de nHAp se realizó mediante una solución acuosa dehidróxido de calcio [Ca(OH)2] y ácido ortofosfórico (H3PO4). Para analizar suefecto biológico, se estableció un bioensayo con siete tratamientos en semillasde rábano con las siguientes concentraciones: control (agua destilada, T1); 25(T2); 50 (T3); 100 (T4); 200 (T5); 500 (T6) y 1 000 mg L-1 (T7); las plántulas sedesarrollaron hasta los siete días después de la siembra. Los resultados muestranque una concentración de 1 000 mg L-1 redujo la germinación en 14,4% encomparación con el tratamiento control (0 mL-1). Mientras que el vigor de lasplántulas se redujo 11.2% con 500 mg L-1. La plúmula y radícula no mostrarondiferencias significativas por los tratamientos con respecto al control, sin embargo,se observó una diferencia estadística con las dosis de 25 y 200 mg L-1, alinhibir y promover respectivamente el crecimiento de las plántulas. Se observóque altas concentraciones de nHAp generaban efectos adversos en las semillas.Finalmente, las nHAp estimularon la producción de biomasa.

11 pags., 8 figs., 2tabs., 1 app., The computationally-aided photophysical and lasing properties of a selected battery of BOPHYs are described and compared to those of related BODIPY counterparts. The present joined theoretical-experimental study helps to put into context the weaknesses and strengths of both dye families under different irradiation conditions. The chemical versatility of the BOPHY scaffold has been also comparatively explored to modulate key photonic properties towards the development of red-emitting dyes, chiroptical dyes and singlet oxygen photosensitizers. Thus, BOPHY BINOLation by fluorine substitution with enantiopure BINOLs endows the BOPHY chromophore with chiroptical activity, as supporting by the simulated circular dichroism, decreasing deeply its fluorescent response due to the promotion of fluorescence-quenching intramolecular charge transfer (ICT). Interestingly, the sole alkylation of the BOPHY core strongly modulates the promotion of ICT, allowing the generation of highly bright BINOL-based BOPHY dyes. Moreover, 3,3′-dibromoBINOLating BOPHYs can easily achieve singlet-oxygen photogeneration, owing to spin-orbit coupling mediated by heavy-atom effect feasible in view of the theoretically predicted disposition of the bromines surrounding the chromophore. From this background, we have established the master guidelines to design bright fluorophores and laser dyes, photosensitizers for singlet oxygen production and chiroptical dyes based on BOPHYs. The possibility to finely mix and balance such properties in a given molecular scaffold outstands BOPHYs as promising dyes competing with the well-settled BODIPY dyes., Financial support from MINECO (MAT2017-83856-C3-1-P, -2-P and-3-P) and Gobierno Vasco (IT912-16) is gratefully acknowledged. G.M.thanks the NIH, Minority Biomedical Research Support (1 SC3GM089589-08), and the Henry Dreyfus Teacher-Scholar Award forfi-nancial support. E.A.Z. and R.S.L. thank Gobierno Vasco for a pre-doctoral fellowship and a postdoctoral contract, respectively. J.J.thanks Comunidad de Madrid/UCM for a research contract.

The most investigated materials used as heterogeneous photocatalysts for the formation of high-value chemicals under mild experimental conditions are presented in this survey. Only papers reporting reactions carried out in harmless solvents such as water, the green solvent par excellence, are reported. Metal oxides have been used often, but carbon-based materials such as carbon nitride and graphene, metal nanoparticles, sulphides and selenides also have received a great attention mainly due to their good performances both in partial oxidations and reductions. The results presented indicate that an appropriate choice of the photocatalytic material is the main problem to be faced to efficiently perform the desired photocatalytic synthesis. Moreover, the highly specific nature of the interaction between the surface of the photocatalyst and the molecules involved in the process must be carefully considered in order to maximize conversion and selectivity and to make these processes green and sustainable competitive alternatives to traditional synthetic methods. Many structural and physicochemical parameters can be tailored such as the initial pH in the case of liquid-solid systems, concentration of reagent(s), induction of defects in the photocatalyst, crystallinity, addition of loading or dopant species to tune the opto-electronic features of semiconductors, and specific surface area.

The objective of this study was to determine the oxidative stress and the physiological and antioxidant responses of coriander plants (Coriandrum sativum) grown for 58 days in soil with zinc oxide nanoparticles (ZnO NPs) and zinc sulfate (ZnSO4) at concentrations of 0, 100, 200, 300, and 400 mg of Zn/kg of soil. The results revealed that all Zn compounds increased the total chlorophyll content (CHLt) by at least 45%, compared to the control group, however, with 400 mg/kg of ZnSO4, chlorophyll accumulation decreased by 34.6%. Zn determination by induction-plasma-coupled atomic emission spectrometry (ICP–AES) showed that Zn absorption in roots and shoots occurred in plants exposed to ZnSO4 at all concentrations, which resulted in high levels of hydrogen peroxide (H2O2) and malondialdehyde (MDA). Only at 400 mg/kg of ZnSO4, a 78.6% decrease in the MDA levels was observed. According to the results, the ZnSO4 treatments were more effective than the ZnO NPs to increase the antioxidant activity of catalase (CAT), ascorbate peroxidase (APX), and peroxidases (POD). The results corroborate that phytotoxicity was higher in plants subjected to ZnSO4 compared to treatments with ZnO NPs, which suggests that the toxicity was due to Zn accumulation in the tissues by absorbing dissolved Zn++ ions.

Background and importance Different studies in the literature have demonstrated promising efficacy of cisplatin–gemcitabine for the treatment of metastatic breast cancer. Real life studies are commonly performed to confirm the results. Aim and objectives To analyse cisplatin–gemcitabine effectiveness and safety in patients with metastatic breast cancer. Material and methods A retrospective observational study was conducted in a university hospital. Patients treated with cisplatin–gemcitabine from January 2007 to February 2020 were included. The following variables were recorded: age, hormone receptor (HR), human epidermal growth receptor-2 (HER2) status, duration of treatment, number of cycles, number and type of previous chemotherapy regimens, progression free survival (PFS) and overall survival (OS), calculated by the Kaplan–Meier method, and adverse events (AEs). Data were obtained from the electronic clinical records and the software where the chemotherapy treatments are registered. Results 56 patients were included, with a median age of 56.5 years (range 30–82). 40 patients (71%) were HR positive, 13 patients (23%) were triple negative and 6 patients (11%) were HER2 positive. At the time of data analysis, one patient was still receiving treatment with cisplatin–gemcitabine and 55 had finished treatment, with a median duration of 2.8 months (4 cycles, range 1–10). Patients had a median of two previous chemotherapy lines in metastatic stage (range 0–4). 85.7% of patients received cisplatin–gemcitabine as metastatic therapy in the secondline or later. The most common regimens used before cisplatin–gemcitabine in metastatic disease were: non-pegylated–liposomal doxorubicin (54.2%), nab–paclitaxel (37.5%), paclitaxel–bevacizumab (35.4%), eribulin (27.1%), epirubicin–docetaxel (18.8%), paclitaxel monotherapy (16.7%), docetaxel monotherapy (14.6%) and pegylated–liposomal doxorubicin (12.5%), with other regimens used less frequently. Median PFS and OS were 3.4 and 6.8 months, respectively. 51.8% of patients had any AE during treatment and the most frequent were anaemia (62%), neutropenia (31%), thrombocytopenia (24%), peripheral neuropathy (17.2%) and asthenia (10.3%). Six patients interrupted their treatment due to AEs. Conclusion and relevance Cisplatin–gemcitabine was shown to be another effective treatment option in metastatic breast cancer. However, several studies in the literature have shown better results for PFS and OS. This may be due to differences in the baseline characteristics of the patients and the use of previous chemotherapy regimens. Cisplatin–gemcitabine was well tolerated and in most cases the AEs did cause interruption of treatment. References and/or acknowledgements Conflict of interest No conflict of interest

Ocean acidification, a phenomenon of seawater pH decrease due to increasing atmospheric CO(2), has a global effect on seawater chemistry, marine biology, and ecosystems. Ocean acidification is a gradual and global long-term process, the study of which demands high-quality pH data. The spectrophotometric technique is capable of generating accurate and precise pH measurements but requires adding an indicator dye that perturbs the sample original pH. While the perturbation is modest in well-buffered seawater, applications of the method in environments with lower buffer capacity such as riverine, estuarine, sea-ice meltwater and lacustrine environments are increasingly common, and uncertainties related to larger potential dye perturbations need further evaluation. In this paper, we assess the effect of purified meta-Cresol Purple (mCP) dye addition on the sample pH and how to correct for this dye perturbation. We conducted numerical simulations by incorporating mCP speciation into the MATLAB CO2SYS program to examine the changes in water sample pH caused by the dye addition and to reveal the dye perturbation mechanisms. Then, laboratory experiments were carried out to verify the simulation results. The simulations suggest that the dye perturbation on sample pH is a result of total alkalinity (TA) contributions from the indicator dye and chemical equilibrium shifts that are related to both the water sample properties (pH, TA, and salinity) and the indicator dye solution properties (pH and solvent matrix). The laboratory experiments supported the simulation results; the same dye solution can lead to different dye perturbations in water samples with different pH, TA, and salinity values. The modeled adjustments agreed well with the empirically determined adjustments for salinities > 5, but it showed greater errors for lower salinities with disagreements as large as 0.005 pH units. Adjustments are minimized when the pH and salinity of the dye are matched to the sample. When the dye is used over a wide range of salinity, we suggest that it should be prepared in deionized water to minimize the dye perturbation effect on pH in the fresher sample waters with less well-constrained perturbation adjustments. We also suggest that the dye perturbation correction should be based on double dye addition experiments performed over a wide range of pH, TA, and salinity. Otherwise, multiple volume dye addition experiments are recommended for each sample to determine the dye perturbation adjustment. We further create a MATLAB function dyeperturbation.m that calculates the expected dye perturbation. This function can be used to validate empirically-derived adjustments or in lieu of empirical adjustments if dye addition experiments are unfeasible (e.g., for historical data). This study of dye perturbation evaluation and correction will improve the accuracy of the pH data, necessary for monitoring the long-term anthropogenic-driven changes in the seawater carbonate system.

ZnO nanoparticles (NPs) were synthesized using zinc acetate dihydrate, ethanol, and oxalic acid as precursor, solvent, and complexing agent, respectively, and urea–hydrogen peroxide (UHP) as, simultaneously, nitrogen precursor and oxygen donor. The structural, morphological, textural, and optical properties of ZnO photocatalysts were investigated using different characterization methods such as XRD, SEM, BET, and UV-Vis-DRS. The XRD patterns showed that the products consisted of ZnO and revealed the presence of nitrogen. SEM images revealed the agglomeration and aggregation of NPs. The photocatalytic activity of ZnO samples was estimated based on the photo-oxidation of 2-propanol under UV irradiation, and ZnO doped with 5%UHP showed higher photocatalytic activity than bare ZnO.

12 pages, 6 figures, 1 table.-- Under a Creative Commons license, The net uptake of carbon dioxide (CO2) from the atmosphere is changing the ocean's chemical state. Such changes, commonly known as ocean acidification, include a reduction in pH and the carbonate ion concentration ([CO32−]), which in turn lowers oceanic saturation states (Ω) for calcium carbonate (CaCO3) minerals. The Ω values for aragonite (Ωaragonite; one of the main CaCO3 minerals formed by marine calcifying organisms) influence the calcification rate and geographic distribution of cold-water corals (CWCs), important for biodiversity. Here, high-quality measurements, collected on thirteen cruises along the same track during 1991–2018, are used to determine the long-term changes in Ωaragonite in the Irminger and Iceland Basins of the North Atlantic Ocean, providing the first trends of Ωaragonite in the deep waters of these basins. The entire water column of both basins showed significant negative Ωaragonite trends between −0.0014 ± 0.0002 and −0.0052 ± 0.0007 per year. The decrease in Ωaragonite in the intermediate waters, where nearly half of the CWC reefs of the study region are located, caused the Ωaragonite isolines to rapidly migrate upwards at a rate between 6 and 34 m per year. The main driver of the decline in Ωaragonite in the Irminger and Iceland Basins was the increase in anthropogenic CO2. But this was partially offset by increases in salinity (in Subpolar Mode Water), enhanced ventilation (in upper Labrador Sea Water), and increases in alkalinity (in classical Labrador Sea Water, cLSW; and overflow waters). We also found that water mass aging reinforced the Ωaragonite decrease in cLSW. Based on these Ωaragonite trends over the last three decades, we project that the entire water column of the Irminger and Iceland Basins will likely be undersaturated for aragonite when in equilibrium with an atmospheric mole fraction of CO2 (xCO2) of ~880 ppmv, corresponding to climate model projections for the end of the century based on the highest CO2 emission scenarios. However, intermediate waters will likely be aragonite undersaturated when in equilibrium with an atmospheric xCO2 exceeding ~630 ppmv, an xCO2 level slightly above that corresponding to 2 °C global warming, thus exposing CWCs inhabiting the intermediate waters to undersaturation for aragonite, The research leading to these results was supported through the EU FP7 project CARBOCHANGE “Changes in carbon uptake and emissions by oceans in a changing climate”, which received funding from the European Commission's Seventh Framework Programme under grant agreement No 264879. For this work, M.I. García-Ibáñez and A. Velo were supported by the BOCATS2 Project (PID2019-104279GB-C21) co-funded by the Spanish Government and the Fondo Europeo de Desarrollo Regional (FEDER). M.I. Garcia-Ibanez was also supported by the UK's Natural Environment Research Council CUSTARD grant [NE/P021263/1], part of the RoSES programme. N.R. Bates was funded by National Science Foundation award (OCE–1258622). M. Fontela was funded by Portuguese national funds from the FCT–Foundation for Science and Technology through project UID/Multi/04326/2019 and CEECINST/00114/2018. This project has also received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 820989 (project COMFORT, Our common future ocean in the Earth system – Quantifying coupled cycles of carbon, oxygen, and nutrients for determining and achieving safe operating spaces with respect to tipping points)

Heterogeneous TiO2 photocatalysis is a promising technology based on the capability of the semiconducting material to generate charges upon irradiation of suitable energy. The photogenerated electrons and holes, in turn, induce redox reactions involving species adsorbed on the surface of the photocatalyst, giving rise to chemical transformations. The presence of highly oxidizing radicals, thus generated, has long led to consider TiO2 photocatalysis only a nonselective oxidation process. In fact, so far it is possible to find in the literature many examples of its use in the field of environmental remediation aimed at the degradation of harmful molecules, although the studies are almost all limited to the laboratory scale. However, selective synthetic reactions can also be carried out both in organic solvents and in water, carefully tuning the crystallinity and surface physicochemical properties of the photocatalyst. Oxidation, reduction, and coupling reactions, together with fuels production, for example, have been reported under mild experimental conditions, using both artificial and sunlight. The efficiency of TiO2 photocatalysis for production of fine chemicals can be further improved by tuning some parameters such as the setup configuration and the reactor geometry and by coupling photocatalysis with a membrane separation unit. The present chapter reports various examples of photocatalytic reactions in the presence of TiO2 photocatalyst, and among them oxidation of alcohols to aldehydes, hydroxylation of aromatic compounds, epoxidation of alkenes, hydrogenation of carbon–carbon multiple bonds, and some types of alkylation reactions will be presented.

Acyl-CoA synthetase 4 (Acsl4), an enzyme involved in arachidonic acid (AA) metabolism, participates in physiological and pathological processes such as steroidogenesis and cancer. The role of Acsl4 in neurons and in nervous system development has also been documented but little is known regarding its functionality in glial cells. In turn, several processes in glial cells, including neurosteroidogenesis, stellation and AA uptake, are regulated by cyclic adenosine monophosphate (cAMP) signal. In this context, the aim of this work was to analyze the expression and functional role of Acsl4 in primary rat astrocyte cultures and in the C6 glioma cell line by chemical inhibition and stable silencing, respectively. Results show that Acsl4 expression was regulated by cAMP in both models and that cAMP stimulation of steroidogenic acute regulatory protein mRNA levels was reduced by Acsl4 inhibition or silencing. Also, Acsl4 inhibition reduced progesterone synthesis stimulated by cAMP and also affected cAMP-induced astrocyte stellation, decreasing process elongation and increasing branching complexity. Similar effects were observed for Acsl4 silencing on cAMP-induced C6 cell morphological shift. Moreover, Acsl4 inhibition and silencing reduced proliferation and migration of both cell types. Acsl4 silencing in C6 cells reduced the capacity for colony proliferation and neurosphere formation, the latter ability also being abolished by Acsl4 inhibition. In sum, this work presents novel evidence of Acsl4 involvement in neurosteroidogenesis and the morphological changes of glial cells promoted by cAMP. Furthermore, Acsl4 participates in migration and proliferation, also affecting cell self-renewal. Altogether, these findings provide insights into Acsl4 functions in glial cells.

Background A common polymorphism (1245A>C) in the HSD3B1 gene is associated with increased de novo synthesis of androgens and worse outcomes in men treated with androgen-deprivation therapy for metastatic castration-sensitive prostate cancer. The objective of the study was to determine whether this polymorphism is associated with outcomes for metastatic castration-resistant prostate cancer (mCRPC) treated with abiraterone or enzalutamide. Patients and methods A total of 547 patients treated with abiraterone or enzalutamide from two prospective cohorts were evaluated. The HSD3B1 genotype was determined by targeted sequencing and/or TaqMan single-nucleotide polymorphism genotyping. In cohort 1, patients were randomized to receive abiraterone + prednisone or enzalutamide. In cohort 2, patients received either agent according to investigator's choice. Prostate-specific antigen (PSA) response rate, time to PSA progression (TTPP), time to progression (TTP) and overall survival were determined. Associations between HSD3B1 genotypes and outcomes were evaluated via univariate Cox regression. Multivariable Cox model was used to determine the independent association of each covariate. Results The HSD3B1 variant genotype (CC) was present in 15% of patients and was associated with worse TTP [hazard ratio (HR) 1.31, 95% confidence interval (CI) 1.02–1.67, P = 0.032] and PSA response rates (48% for CC versus 62% and 65% for AA and AC, respectively [P = 0.019]), with no significant difference in TTPP (HR 1.28, 95% CI 0.99–1.66, P = 0.064). The effect of genotype was similar for treatment with abiraterone or enzalutamide with a negative test for interaction for TTPP (P = 0.997) and TTP (P = 0.749). Multivariable analysis did not show a significant association between genotype and TTP or TTPP. Conclusions The HSD3B1 (CC) genotype was associated with shorter TTP and lower PSA response rate in patients with mCRPC treated with abiraterone or enzalutamide. However, the CC genotype did not provide prognostic information beyond that conferred by standard clinical variables, suggesting that it may not be a suitable stand-alone biomarker in mCRPC.

Copper nanoparticles (NCu) were synthetized and added to commercial glass ionomer cement, to evaluate in vitro its antibacterial activity against oral cavity strains. The NCu were synthesized by copper acetate reduction with L-ascorbic acid and characterized by FTIR, Raman, XPS, XRD and TEM. Then, commercial glass ionomer cement (GIC) was modified (MGIC) with various concentrations of NCu and physicochemically characterized. Cell viability was tested against human dental pulp fibroblasts (HDPFs) by Alamar-Blue assay and antibacterial test was performed against S. mutans and S. sanguinis by colony forming unit (CFU) growth method. Synthesized NCu rendered a mixture of both metallic copper and cuprous oxide (Cu2O). HDPF viability reduces with exposure time to the extracts (68-72% viability) and MGIC with 2-4 wt% NCu showed antimicrobial activity against the two tested strains.

The photocatalytic oxidation of 5-hydroxymethyl-2-furfural (HMF) under natural solar irradiation was carried out in liquid– solid regime by using a batch reactor. Home prepared meso-tetra aryl substituted porphyrins (Pps) whether metal-free ( H2Pp) or containing Cu(II) or Zn(II) complexes (CuPp, ZnPp), opportunely functionalized with lipophilic [(3-n-pentadecylphenoxyethoxy)-] chains, were supported on graphitic (g-C3N4) or thermo-exfoliated carbon nitride ( C3N4-TE) to obtain a set of heterogeneous photocatalysts. The loading of the Pps on both carbon nitrides was 6 μmol per gram of support. During the experiments all the photocatalysts resulted active for the conversion of HMF, and in all cases its partial oxidation product, 2,5-furandicarboxyaldehyde (FDC), was selectively obtained in the aqueous suspension. Both carbon nitrides played the key role as photocatalysts whereas the presence of porphyrin improved the visible light absorption. The presence of the metalporphyrin in the composite slightly increased the selectivity to FDC. The best compromise between selectivity to FDC (36%) and conversion of HMF (73%) was obtained in the presence of the ZnPp-C3N4-TE photocatalyst at natural pH. Moreover, at pH 9 the CuPp-C3N4-TE sample showed the best performances, indicating that the pH can affect the photocatalytic activity of the samples towards the partial selective oxidation of HMF to FDC.

The bacterial colonization of absorbable membranes used for guided tissue regeneration (GTR), as well as their rapid degradation that can cause their rupture, are considered the major reasons for clinical failure. To address this, composite membranes of polycaprolactone (PCL) and gelatin (Gel) loaded with zinc oxide nanoparticles (ZnO-NPs; 1, 3 and 6 wt% relative to PCL content) were fabricated by electrospinning. To fabricate homogeneous fibrillar membranes, acetic acid was used as a sole common solvent to enhance the miscibility of PCL and Gel in the electrospinning solutions. The effects of ZnO-NPs in the physico-chemical, mechanical and in vitro biological properties of composite membranes were studied. The composite membranes showed adequate mechanical properties to offer a satisfactory clinical manipulation and an excellent conformability to the defect site while their degradation rate seemed to be appropriate to allow successful regeneration of periodontal defects. The presence of ZnO-NPs in the composite membranes significantly decreased the planktonic and the biofilm growth of the Staphylococcus aureus over time. Finally, the viability of human osteoblasts and human gingival fibroblasts exposed to the composite membranes with 1 and 3 wt% of ZnO-NPs indicated that those membranes are not expected to negatively influence the ability of periodontal cells to repopulate the defect site during GTR treatments. The results here obtained suggest that composite membranes of PCL and Gel loaded with ZnO-NPs have the potential to be used as structurally stable GTR membranes with local antibacterial properties intended for enhancing clinical treatments.

Alkaline (or geopolymer) cements have proven to be a sustainable alternative to the ordinary portland cement material. The laboratory reagents normally used as alkaline activators constitute the most costly and on occasion polluting constituents of such cementitious systems. This study aimed to explore the use of a disposed cleaning solution (CS), coming from the aluminium transformation industry, as an activator for high and low calcium aluminosilicate precursors. For that a Blast Furnace Slag (BFS) and a type F-Fly Ash (FA) were used. Precursors activated with a traditional NaOH solutions were used as a reference. Kinetics of reactions (isothermal calorimetry) were evaluated and mechanical strength of hardened pastes determined. The nature of the reaction products generated in this new systems were also identified by using XRD, FTIR, SEM and 29Si and 27Al MAS NMR. The findings showed that the CS can be effectively used to prepare cementitious materials, particularly when applied to CaO-SiO2-Al2O3 system precursors such as BFS, which require lower alkalinity than FA-based precursors. The nature of the reaction products generated in the CS alkali activated systems was similar than those observed in the reference systems, however Al richer reaction products were observed in the former., This research was funded by the Spanish Ministry of Science, Innovation and Universities under project BIA2016-76466-R and ERDF under project RTC2016-4872-S (principal investigators Angel Palomo and Ana Fernandez-Jimenez). In addition, thanks the project from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 734833.

We investigate the relation between the detection of the 11.3 μm polycyclic aromatic hydrocarbon (PAH) feature in the nuclear (∼24-230 pc) regions of 22 nearby Seyfert galaxies and the properties of the cold molecular gas. For the former we use ground-based (0.3-0.6″ resolution) mid-infrared (mid-IR) spectroscopy. The cold molecular gas is traced by ALMA and NOEMA high (0.2-1.1″) angular resolution observations of the CO(2-1) transition. Galaxies with a nuclear detection of the 11.3 μm PAH feature contain more cold molecular gas (median 1.6 × 107 MO ) and have higher column densities (N(H2) = 2 × 1023 cm-2) over the regions sampled by the mid-IR slits than those without a detection. This suggests that molecular gas plays a role in shielding the PAH molecules in the harsh environments of Seyfert nuclei. Choosing the PAH molecule naphthalene as an illustration, we compute its half-life in the nuclear regions of our sample when exposed to 2.5 keV hard X-ray photons. We estimate shorter half-lives for naphthalene in nuclei without a 11.3 μm PAH detection than in those with a detection. The Spitzer/IRS PAH ratios on circumnuclear scales (∼4″ ∼ 0.25-1.3 kpc) are in between model predictions for neutral and partly ionized PAHs. However, Seyfert galaxies in our sample with the highest nuclear H2 column densities are not generally closer to the neutral PAH tracks. This is because in the majority of our sample galaxies, the CO(2-1) emission in the inner ∼4″ is not centrally peaked and in some galaxies traces circumnuclear sites of strong star formation activity. Spatially resolved observations with the MIRI medium-resolution spectrograph on the James Webb Space Telescope will be able to distinguish the effects of an active galactic nucleus (AGN) and star formation on the PAH emission in nearby AGN., With funding from the Spanish government through the "María de Maeztu Unit of Excellence" accreditation (MDM-2017-0737)

The Keggin heteropolyacid (HPA), H3PW12O40 (PW12) has been supported on commercial boron nitride (BN) and two types of home prepared carbon nitride (C3N4). The supported PW12 was used in the gas-solid (photo)catalytic 2-propanol dehydration reaction to give propene at atmospheric pressure and temperatures in the range 70–120 °C and resulted more active than the pristine PW12. Reaction rate increased by increasing the temperature. Noticeably, the propene formation rate was higher by irradiating the catalytic system. The PW12/BN material resulted more active than PW12/C3N4. The acidity of the HPA cluster accounts for the catalytic role, whereas both the acidity and the redox properties of the HPA species were responsible for the increase of the reaction rate in the photo-assisted catalytic reaction.