Polymeric foams as the matrix of voltammetric sensors for the detection of catechol, hydroquinone, and their mixtures

Producción CientíficaPorous electrodes based on polymethylmethacrylate and graphite foams (PMMA_G_F) have been developed and characterized. Such devices have been successfully used as voltammetric sensors to analyze catechol, hydroquinone, and their mixtures. The presence of pores induces important changes in the oxidation/reduction mechanism of catechol and hydroquinone with respect to the sensing properties observed in nonfoamed PMMA_graphite electrodes (PMMA_G). The electropolymerization processes of catechol or hydroquinone at the electrode surface observed using PMMA_G do not occur at the surface of the foamed PMM_G_F. In addition, the limits of detection observed in foamed electrodes are one order of magnitude lower than the observed in the nonfoamed electrodes. Moreover, foamed electrodes can be used to detect simultaneously both isomers and a remarkable increase in the electrocatalytic properties shown by the foamed samples, produces a decrease in the oxidation potential peak of catechol in presence of hydroquinone, from +0.7 V to +0.3 V. Peak currents increased linearly with concentration of catechol in presence of hydroquinone over the range of 0.37·10−3 M to 1.69·10−3 M with a limit of detection (LOD) of 0.27 mM. These effects demonstrate the advantages obtained by increasing the active surface by means of porous structures.Ministerio de Economía, Industria y Competitividad - Fondo Europeo de Desarrollo Regional (project AGL2015-67482-R)Junta de Castilla y Leon - Fondo Europeo de Desarrollo Regional (project VA-011U16

Simultaneous Determination of Pesticides in Fruits by Using Second-Order Fluorescence Data Resolved by Unfolded Partial Least-Squares Coupled to Residual Bilinearization

In the present work, a chemometric-assisted spectrofluorimetric method has been developed for the simultaneous determination of natural fluorescent pesticides, carbaryl, carbendazim, and thiabendazole, in orange and banana. Only a simple extraction with methanol was required as sample pretreatment. Emission-excitation fluorescence matrices were obtained and resolved by using a second-order multivariate calibration method based on unfolded partial least-squares combined with residual bilinearization (U-PLS/RBL) for achieving “second-order advantage.” In this way, pesticides were determined in fruits even in the presence of inner filter effects, background interactions, strong spectral overlapping, and unexpected components. U-PLS can cope with effects that cause trilinearity loss such as, inner filter effects, including background in the calibration set; meanwhile, RBL allows to resolve the presence of unexpected components. The extraction technique was validated against a commonly applied technique based on the use of ethyl acetate and sodium sulfate. Besides, results obtained for real samples were statistically compared with those obtained by using HPLC. LODs of 0.038, 0.054, and 0.018 mg•kg−1 and 0.044, 0.072, and 0.020 mg•kg−1 were obtained for carbaryl, carbendazim, and thiabendazole in banana and orange samples, respectively; values were in accordance with the MRLs (Maximum Residue Limits) established by different official control organizations such as National Food Safety and Quality Service (SENASA), Codex Alimentarius (based on Food and Agriculture Organization (FAO) of the United Nations and World Health Organization (WHO), and Environmental Protection Agency (EPA).National University of Rosario, Faculty of Biochemical and Pharmaceutical Sciences, Rosario, Argentina BIO 253 BIO 415Argentine Catholic University, Faculty of Chemistry and Engineering, Rosario, ArgentinaCONICET (National Centre of Scientific and Technical Research)ANPCyT (National Agency of Scientific and Technological Promotion

RANS simulations of wind flow at the Bolund experiment

As part of their development, the predictions of numerical wind flow models must be compared with measurements in order to estimate the uncertainty related to their use. Of course, the most rigorous such comparison is under blind conditions. The following paper includes a detailed description of three different wind flow models, all based on a Reynolds-averaged Navier-Stokes approach and two-equation k-ε closure, that were tested as part of the Bolund blind comparison (itself based on the Bolund experiment which measured the wind around a small coastal island). The models are evaluated in terms of predicted normalized wind speed and turbulent kinetic energy at 2 m and 5 m above ground level for a westerly wind direction. Results show that all models predict the mean velocity reasonably well; however accurate prediction of the turbulent kinetic energy remains achallenge

The elusive nature of the r-stars

R stars are carbon stars, less luminous and hotter than the carbon stars evolving along the AGB phase. Thus, their carbon enrichment cannot be a consequence of the third dredge-up, a fact also in agreement with the lack of s-element enhancements in their envelopes. Since their discovery the absence of binaries has lead to the conclusion that a previous merger might play a fundamental role in the observed chemical composition, likely through non-standard mixing at the time of the He-flash. On the other hand numerical simulations, in which the He-flash is artificially located close to the edge of a degenerate He core, have successfully induced mixing of carbon into the envelope. In this context it has been suggested that the merger of a degenerate He core with that of a normal red giant star could lead to the formation of a rapidly rotating core undergoing o -centre He ignition in highly degenerate conditions. This scenario is also supported by statistical analysis of the potential mergers that could explain the number, and location in the Galaxy, of observed R stars. Basing on detailed stellar models we will show the evolution of these mergers, that are very common in nature, and do not seem to be the progenitors of (hot) R stars.Postprint (published version

Analysis of milk using a portable potentiometric electronic tongue based on five polymeric membrane sensors

Producción CientíficaA portable potentiometric electronic tongue (PE-tongue) was developed and applied to evaluate the quality of milk with different fat content (skimmed, semi-skimmed, and whole) and with different nutritional content (classic, calcium-enriched, lactose-free, folic acid–enriched, and enriched in sterols of vegetal origin). The system consisted of a simplified array of five sensors based on PVC membranes, coupled to a data logger. The five sensors were selected from a larger set of 20 sensors by applying the genetic algorithm (GA) to the responses to compounds usually found in milk including salts (KCl, CaCl2, and NaCl), sugars (lactose, glucose, and galactose), and organic acids (citric acid and lactic acid). Principal component analysis (PCA) and support vector machine (SVM) results indicated that the PE-tongue consisting of a five-electrode array could successfully discriminate and classify milk samples according to their nutritional content. The PEtongue provided similar discrimination capability to that of a more complex system formed by a 20-sensor array. SVM regression models were used to predict the physicochemical parameters classically used in milk quality control (acidity, density, %proteins, %lactose, and %fat). The prediction results were excellent and similar to those obtained with a much more complex array consisting of 20 sensors. Moreover, the SVM method confirmed that spoilage of unsealed milk could be correctly identified with the simplified system and the increase in acidity could be accurately predicted. The results obtained demonstrate the possibility of using the simplified PE-tongue to predict milk quality and provide information on the chemical composition of milk using a simple and portable system.Ministerio de Asuntos Económicos y Transformación Digital y FEDER (grant RTI 2018-097990-B-100)Junta de Castilla y Leon-FEDER (grant VA275P18) and (Infraestructuras Red de Castilla y León (INFRARED UVA01

Serial block-face scanning electron microscopy applied to study the trafficking of 8D3-coated gold nanoparticles at the blood-brain barrier

Due to the physical and physiological properties of the blood-brain barrier (BBB), the transport of neurotherapeutics from blood to brain is still a pharmaceutical challenge. We previously conducted a series of experiments to explore the potential of the anti-transferrin receptor 8D3 monoclonal antibody (mAb) to transport neurotherapeutics across the BBB. In that study, gold nanoparticles (AuNPs) were coated with the 8D3 antibody and administered intravenously to mice. Transmission electron microscopy was used and a two-dimensional (2D) image analysis was performed to detect the AuNPs in the brain capillary endothelial cells (BCECs) and brain parenchyma. In the present work, we determined that serial block-face scanning electron microscopy (SBF-SEM) is a useful tool to study the transcytosis of these AuNPs across the BBB in three dimensions and we, therefore, applied it to gain more knowledge of their transcellular trafficking. The resulting 3D reconstructions provided additional information on the endocytic vesicles containing AuNPs and the endosomal processing that occurs inside BCECs. The passage from 2D to 3D analysis reinforced the trafficking model proposed in the 2D study, and revealed that the vesicles containing AuNPs are significantly larger and more complex than described in our 2D study. We also discuss tradeoffs of using this technique for our application, and conclude that together with other volume electron microscopy imaging techniques, SBF-SEM is a powerful approach that is worth of considering for studies of drug transport across the BBB

Priming by Chemokines Restricts Lateral Mobility of the Adhesion Receptor LFA-1 and Restores Adhesion to ICAM-1 Nano-Aggregates on Human Mature Dendritic Cells

LFA-1 is a leukocyte specific β2 integrin that plays a major role in regulating adhesion and migration of different immune cells. Recent data suggest that LFA-1 on mature dendritic cells (mDCs) may function as a chemokine-inducible anchor during homing of DCs through the afferent lymphatics into the lymph nodes, by transiently switching its molecular conformational state. However, the role of LFA-1 mobility in this process is not yet known, despite that the importance of lateral organization and dynamics for LFA-1-mediated adhesion regulation is broadly recognized. Using single particle tracking approaches we here show that LFA-1 exhibits higher mobility on resting mDCs compared to monocytes. Lymphoid chemokine CCL21 stimulation of the LFA-1 high affinity state on mDCs, led to a significant reduction of mobility and an increase on the fraction of stationary receptors, consistent with re-activation of the receptor. Addition of soluble monomeric ICAM-1 in the presence of CCL21 did not alter the diffusion profile of LFA-1 while soluble ICAM-1 nano-aggregates in the presence of CCL21 further reduced LFA-1 mobility and readily bound to the receptor. Overall, our results emphasize the importance of LFA-1 lateral mobility across the membrane on the regulation of integrin activation and its function as adhesion receptor. Importantly, our data show that chemokines alone are not sufficient to trigger the high affinity state of the integrin based on the strict definition that affinity refers to the adhesion capacity of a single receptor to its ligand in solution. Instead our data indicate that nanoclustering of the receptor, induced by multi-ligand binding, is required to maintain stable cell adhesion once LFA-1 high affinity state is transiently triggered by inside-out signals.Peer ReviewedPostprint (published version

Análisis de las diferencias motivacionales entre el fútbol 7 y el fútbol 11

El objeto de este estudio es analizar las diferencias motivacionalesque existen entre el fútbol 7 y el fútbol 11. Para ello trabajamos con unamuestra de 183 futbolistas masculinos pertenecientes a tres clubes de fútbolbase entre 8 y 18 años, a los cuáles se les administraron un Cuestionario Sociodemográfico,la Escala de Orientación Motivacional en el Deporte de Weiss,Bredemeier y Shewchuk, (1985), el Cuestionario de Orientación a la Tareay al Ego de Duda y Nicholls, (1989) y la Escala de Habilidad Física Percibidade Ryckman, Robbins, Thornton y Cantrell (1982). Los participantes,tanto en fútbol 7 como en fútbol 11, mostraron una mayor orientación a latarea que al ego, estaban más motivados intrínseca que extrínsecamente yposeían unos valores medio-altos en habilidad física percibida tanto generalcomo específica. Los sujetos pertenecientes a la modalidad de fútbol 7obtuvieron valores más elevados en orientación a la tarea 8,85 (±1,13), enmotivación intrínseca 8,64 (±1,10) y en habilidad física percibida general7,45 (±1,03) y específica 7,52 (±1,81), escalas que indican y aseguran la permanenciaen la práctica, aunque también alcanzaron mayor puntuación quelos practicantes de fútbol 11 en orientación al ego 5,34 (±2,32), motivaciónextrínseca 7,44 (±1,77) y amotivación 3,21 (±2,06), lo que podría atribuirsea que son deportistas con un bagaje de experiencias aún corto en el fútboly con un conocimiento no demasiado elevado del deporte en sí