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Ionic liquids are a promising alternative to common organic electrolytes in sodium-ion batteries that offer a unique combination of physical and chemical properties, leading to the development of h...

This study successfully applied a potentiometric E-tongue with 20 cross-selectivity lipidic polymeric membranes in the discrimination of three semi-quantitative groups, that represented the following intervals of honey adulteration percentage with cane sugar: 0 %; [0, 10]%; [10, 20]% of adulteration. We analysed five different types of Portuguese honey; five brands of cane sugar were added to the adulterated samples; a comparative analysis was then performed. Linear discriminant analysis coupled with a tabu search algorithm for feature selection was applied to the ETongue's analytical data to select the best model. A discriminant model with 12 sensors was obtained. This model classified correctly all samples in both in internal (train data, 15 samples) and external validation (test data,10 samples). Also, multiple linear regression with tabu search was applied to verify if ETongue's data would allow quantifying the honey's adulteration level. The results showed that it was possible to obtain a quantitative model but with unsatisfactory predictive performance in the test data group (external validation), giving, in general, values below the expected concentrations. E-tongue is a real-time green, flexible and low-cost analytical tool that requires minimum sample preparation and no special technical skills, being a promising tool for everyday application.

The present study established multiple linear regression models using two ultrasound in vivo measurements (at lumbar and sternal regions, with different real-time ultrasonography machines and probes) and live weight, to predict simultaneously carcass composition and body fat depots of different breeds of sheep and goat. This study is important for the small ruminant industry, considering the feasibility of using the ultrasound methodology in field conditions, as well as an online system of the carcass evaluation. The multiple linear regression models were obtained by selecting the best subset of variables between using the in vivo measurements (raw variables), their second degree and interactions, evaluated in terms of prediction performance using cross-validation “K-folds” and validated by a test group. Overall, high accuracy (adj R2) was obtained from the linear relationship between predicted and experimental values of the group test for each of the nine dependent variables, with values varying between adj R2 0.88 and 0.98. The authors are grateful to Laboratory of Carcass and Meat Quality of Agriculture School of Polytechnic Institute of Bragança ‘Cantinho do Alfredo’. The authors are members of the CYTED network HEALTHY MEAT (119RT0568). info:eu-repo/semantics/publishedVersion

This study aimed to characterize honey of Melipona scutellaris regarding its physicochemical parameters using the electronic tongue (e-tongue) technique combined with the multivariate statistical analysis for honey differentiation. Physicochemical parameters were evaluated following official methods of chemical analyses. A potentiometric electronic tongue with 16 cross-sensitivity sensors was used for the analysis. The Principal Component Analysis and the Cluster Analysis distinguished two groups for the sample set in the evaluation of physicochemical parameters, similar to results found using the electronic tongue. We verified a correlation greater than 0.70 between the profile of potentiometric signals and values of pH, ashes, electrical conductivity, HMF, diastase activity, reducing sugars, and apparent sucrose. The combined use of the electronic tongue with the statistical analysis showed the similarity between samples through the formation of two groups of the sample set. The electronic tongue may be used as a complement to traditional techniques of analyses to determine honey physicochemical parameters, constituting a promising tool in association with the multivariate statistical analysis. This study was financed in part by the “Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - Brasil” (CAPES) - Finance Code 001 and by the “Fundação de Amparo à Pesquisa do Estado da Bahia” (FAPESB) - under grant PAM0004/2014. We thank “Conselho Nacional de Desenvolvimento Científico e Tecnológico” (CNPq) for the scholarship granted to CALC (No. 305885/2017-0). info:eu-repo/semantics/publishedVersion

Made available in DSpace on 2022-04-28T19:43:37Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-10-15 Tebuconazole (TEB) is a chiral triazole fungicide worldwide employed to control plant pathogens and preserve wood. People can be exposed to TEB either through diet and occupational contamination. This work investigates the in vitro inhibitory potential of rac-TEB, S-(+)-TEB, and R-(−)-TEB over the main cytochrome P450 enzymes (CYP450) using human liver microsomes to predict TEB in vivo inhibition potential. The IC50 values showed that in vitro inhibition was enantioselective for CYP2C9, CYP2C19, and CYP2D6, but not for CYP3A4/5. Despite enantioselectivity, rac-TEB and its single enantiomers were always classified in the same category. The inhibition mechanisms and constants were determined for rac-TEB and it has shown to be a mixed inhibitor of CYP3A4/5 (Ki = 1.3 ± 0.3 μM, αKi = 3.2 ± 0.5 μM; Ki = 0.6 ± 0.3 μM, αKi = 1.3 ± 0.3 μM) and CYP2C9 (Ki = 0.7 ± 0.1 μM, αKi = 2.7 ± 0.5 μM), and a competitive inhibitor of CYP2D6 (Ki = 11.9 ± 0.7 μM) and CYP2C19 (Ki = 0.23 ± 0.02 μM), respectively, suggesting that in some cases, rac-TEB has a higher or comparable inhibitory potential than well-known strong inhibitors of CYP450 enzymes, especially for CYP2C9 and CYP2C19. In vitro-in vivo extrapolations (IVIVE) were conducted based on the results and data available in the literature about TEB absorption and metabolism. R1 values were estimated based on the Food and Drug Administration guideline and suggested that in a chronic oral exposure scenario considering the acceptable daily intake dose proposed by the European Food and Safety Authority, the hypothesis of rac-TEB to inhibit the activities of CYP3A4/5, CYP2C9, and CYP2C19 in vivo and cause pesticide-drug interactions cannot be disregarded. Departamento de Química Faculdade de Filosofia Ciências e Letras de Ribeirão Preto Universidade de São Paulo Departamento de Física e Química Faculdade de Ciências Farmacêuticas de Ribeirão Preto Universidade de São Paulo National Institute for Alternative Technologies of Detection Toxicological Evaluation and Removal of Micropollutants and Radioactives (INCT–DATREM) Unesp Institute of Chemistry, P.O. Box 355 National Institute for Alternative Technologies of Detection Toxicological Evaluation and Removal of Micropollutants and Radioactives (INCT–DATREM) Unesp Institute of Chemistry, P.O. Box 355

We have performed molecular dynamics (MD) simulations of 1-ethyl-3-methylimidazolium tetracyanoborate ([EMIM]+[B(CN)4]-) ionic liquid to investigate the impact of addition of Na+/K+[B(CN)4]- salts and poly(ethylene oxide) (PEO6) on transport properties. These ternary mixtures are promising electrolyte materials for Na+-ion and K+-ion batteries as alternatives to the traditional Li+-ion ones. In addition, local structure was assessed through radial distribution functions. Our main findings are the following: (1) when compared to systems with larger amounts of Na+ and K+, it was observed that lower concentrations enhance the overall ionic conductivity and decrease viscosity; (2) Na+ and K+ cations prefer to be coordinated to the polymer chains rather than the [B(CN)4]- anions; (3) transport properties are improved when PEO6 oligomers are included in the electrolyte medium but these improvements continue only up to an optimum amount of PEO6. Beyond this amount, further addition of PEO6 did not have any additional impact on transport properties.

Tebuconazole (TEB) is a chiral triazole fungicide that is globally marketed and used as a racemic mixture to control plant pathogens. Due to its use as a racemic mixture, TEB may exhibit enantioselective toxicokinetics toward nontarget organisms, including humans. Therefore, the in vitro enantioselective metabolism of TEB by cytochrome P450 enzymes (CYP450) was studied using human liver microsomes, and the in vivo toxicokinetic parameters were predicted. A new enantioselective, reversed-phase LC-MS/MS method was developed and validated to analyze the enantiomers of TEB and its main metabolite, 1-hydroxytebuconazole (TEBOH). In vitro metabolic parameters were obtained, and in vitro-in vivo extrapolations were performed. Michaelis-Menten and atypical biphasic kinetic profiles were observed with a total intrinsic clearance ranging from 53 to 19 mL min−1 mg−1. The in vitro-in vivo extrapolation results showed that TEB first passage effect by the liver seems to be negligible, with hepatic clearance and extraction ratios ranging from 0.53 to 5.0 mL min−1 kg−1 and 2.7–25%, respectively. Preferential metabolism of (+)-TEB to rac-TEB and (−)-TEB was observed, with preferential production of (+)-TEBOH. Furthermore, reaction phenotyping studies revealed that, despite the low hepatic clearance in the first pass metabolism of TEB, multiple human CYP450 isoforms were involved in TEB metabolism when TEBOH enantiomers were generated, mainly CYP3A4 and CYP2C9, which makes TEB accumulation in the human body more difficult due to multiple metabolic pathways.

“Bee pollen” is pollen collected from flowers by honey bees. It is used by the bees to nourish themselves, mainly by providing royal jelly and brood food, but it is also used for human nutrition. For the latter purpose, it is collected at the hive entrance as pellets that the bees bring to the hive. Bee pollen has diverse bioactivities, and thus has been used as a health food, and even as medication in some countries. In this paper, we provide standard methods for carrying out research on bee pollen. First, we introduce a method for the production and storage of bee pollen which assures quality of the product. Routine methods are then provided for the identification of the pollen’s floral sources, and determination of the more important quality criteria such as water content and content of proteins, carbohydrates, fatty acids, vitamins, alkaloids, phenolic and polyphenolic compounds. Finally, methods are described for the determination of some important bioactivities of bee pollen such as its antioxidant, anti-inflammatory, antimicrobial and antimutagenic properties. Métodos estándar Para la investigación del polen El "polen de abeja" es el polen recogido de las flores por las abejas melíferas. El polen de abeja es utilizado para nutrir a las propias abejas, principalmente para proporcionar jalea real y alimento para las crías, pero también se utiliza para la nutrición humana. Para este último fin, se recoge en la entrada de la colmena en forma de gránulos que las abejas llevan a la colmena. El polen de abeja tiene diversas bioactividades, por lo que se hautilizado como alimento para la salud, e incluso como medicamento en algunos países. En este artículo, proporcionamos métodos estándar para llevar a cabo investigaciones sobre el polen de abeja. En primer lugar, presentamos un método de producción y almacenamiento de polen de abeja que garantiza la calidad del producto. A continuación, se ofrecen métodos de rutina para la identificación de las fuentes florales del polen y la determinación de los criterios de calidad más importantes, como el contenido de agua y de proteínas, carbohidratos, ácidos grasos, vitaminas, alcaloides y compuestos fenólicos y polifenólicos. Por último, se describen métodos para la determinación de algunas bioactividades importantes del polen de abeja, como sus propiedades antioxidantes, antiinflamatorias, antimicrobianas y antimutagénicas. The COLOSS (Prevention of honey bee COlony LOSSes) Association aims to explain and prevent massive honey bee colony losses. It was funded through the COST Action FA0803. COST (European Cooperation in Science and Technology) is a unique means for European researchers to jointly develop their own ideas and new initiatives across all scientific disciplines through trans-European networking of nationally funded research activities. Based on a pan-European intergovernmental framework for cooperation in science and technology, COST has contributed since its creation more than 40 years ago to closing the gap between science, policy makers and society throughout Europe and beyond. COST is supported by the EU Seventh Framework Program for research, technological development and demonstration activities (Official Journal L 412, 30 December 2006). The European Science Foundation as implementing agent of COST provides the COST Office through an EC Grant Agreement. The Council of the European Union provides the COST Secretariat. The COLOSS network is now supported by the Ricola Foundation – Nature & Culture. Figures 26–28 are reproduced from Sawyer (1981) with the permission of the publishers University College Cardiff Press and Northern Bee Books. Lidia Barreto and J Nordi wish to thank the Apiculture Research Center of Taubate University (UNITAU-SP/Brazil) and Agriculture Secretary of Bahia State (SEAGRI-BA/ BRAZIL). Maria Campos wishes to thank (UI0204): UIDB/ 00313/2020, Center of Chemistry from Faculty of Sciences and Technology of University of Coimbra, Portugal. Of elia Anjos wishes to thank to Forest Research Centre, a research unit funded by Fundac¸~ao para a Ci^encia e a Tecnologia I.P. (FCT), Portugal (UIDB/00239/2020), and to Centro de Biotecnologia de Plantas da Beira Interior for the OPUS software availability. Norma Almaraz Abarca thanks to the Instituto Politecnico Nacional for financial and logistic support. Manuel Chica and Pascual Campoy wish to thank the APIFRESH project. APIFRESH has been co-funded by the European Commission under the R4SMEs 7th Framework Program. Olena Lokutova thanks the Austrian Institute of beekeeping, Dr H Pehhacker and the same members of the Institute H Hagel and E H€uttinger for conducting photomicroscopic studies and pollen analysis Ukrainian samples of pollen loads, which were the basis of the atlas of pollen “honey plants” of Ukraine. Olena is grateful also to Polish colleagues Z Warakomska (Department of Botany University of Lublin) and D Teper (Polish Institute of beekeeping) for their professionalism and consultations to determine the botanical origin of some Ukrainian honey. Also thanks to their scientific advisers’ academician G Bogdanov (National Academy of Agrarian Sciences of Ukraine), Prof. V Polishuk (Department of beekeeping National University of Life and Environmental Sciences of Ukraine) and O Martynyuk (M.G. Kholodny Institute of Botany, Kiev, Ukraine) for his helpful co-operation in the field of beekeeping and palinology. Janka Nozkova wishes to thank the Operational Program Research and Development of the European Regional Development Fund in the frame of the project “Support of technologies innovation for special bio-food products for human healthy nutrition” (ITMS 26220220115) and also by the Excellence Center for Agrobiodiversity Conservation and Benefit – project implemented under the Operational Program Research and Development financed by European Fund for Regional Development ITMS 26220120015 (Slovak Republic) and all colleagues from Institute of Biodiversity and Biosafety, Slovak University of Agriculture in Nitra for their help with image analysis. Ananias Pascoal, Georgina Tolentino and Let ıcia Estevinho would like to thank Fundac¸~ao para a Ci^encia e Tecnologia (FCT), Programa Operacional Pontencial Humano (POPH) and European Union (EU) for his Postdoctoral grant SFRH/BPD/91380/2012. Wiebke Sickel, Markus Ankenbrand, Gudrun Grimmer, Frank F€orster, Ingolf Steffan-Dewenter and Alexander Keller thank the financial support by the DFG Collaborative Research Center 1047, Insect Timing. MJA was further supported by a grant of the German Excellence Initiative to the Graduate School of Life Sciences of the University of W€urzburg. They are grateful to the members of the Departments of Animal Ecology and Tropical Biology; Bioinformatics; and Human Genetics, University of W€urzburg, for constructive input on the design of the workflow. Additionally thank to the Department of Human Genetics, especially S. Rost, for granting access to the Illumina MiSeq device. Zivoslav Te si c, Mirjana Mosi c, Aleksandar Kosti c, Mirjana Pe si c, Du sanka Milojkovi c-Opsenica thank the Ministry of Education, Science and Technological Development of Serbia, Grants 172017 and TR 31069. Gina Tolentino would like to thank the Mountain Research Center (CIMO), Agricultural College of Bragança, Polytechnic Institute of Braganc¸a for his research grant in the project titled " Development of new bee products in biological production way.” info:eu-repo/semantics/publishedVersion

Sodium-ion batteries have a great potential for energy storage applications, however, its realization depends strongly on a deep atomistic understanding of the sodium-ion transport mechanisms, which is a key step to optimize its performance. A complete characterization of sodium-ion transport mechanism requires large time-scale calculations, which is a challenge even for classical atomistic force-field molecular dynamics simulations. Thus, in this work, we performed a calibration of a coarse-grained force-field to describe the thermodynamic and transport properties of sodium-ion for the particular case of cyanoborate-based ionic liquid using different molar fractions of sodium tetracyanoborate salt dissolved in 1-ethyl-3-methyl-imidazolium tetracyanoborate. The results from coarse-grained modeling were found to be in fair agreement with atomistic simulations and experimental data, and they captured concentration dependence of [Nax[Anion]y]x−y aggregate sizes. In particular, two distinct populations of sodium-ions were identified inside the [Nax[Anion]y]x−y aggregates: 1) a slow one in vehicular diffusion and 2) a fast one in hoping diffusion. Both of them contribute to sodium ion transport and occur preferentially at different sodium-ion concentrations. The present findings were obtained for a cyanoborate-based ionic liquid, however, we expect that our insights can be used to understand similar ionic liquids.

Cells challenged by photosensitized oxidations face strong redox stresses and rely on autophagy to either survive or die. However, the use of macroautophagy/autophagy to improve the efficiency of photosensitizers, in terms of inducing cell death, remains unexplored. Here, we addressed the concept that a parallel damage in the membranes of mitochondria and lysosomes leads to a scenario of autophagy malfunction that can greatly improve the efficiency of the photosensitizer to cause cell death. Specific damage to these organelles was induced by irradiation of cells pretreated with 2 phenothiazinium salts, methylene blue (MB) and 1,9-dimethyl methylene blue (DMMB). At a low concentration level (10 nM), only DMMB could induce mitochondrial damage, leading to mitophagy activation, which did not progress to completion because of the parallel damage in lysosome, triggering cell death. MB-induced photodamage was perceived almost instantaneously after irradiation, in response to a massive and nonspecific oxidative stress at a higher concentration range (2 µM). We showed that the parallel damage in mitochondria and lysosomes activates and inhibits mitophagy, leading to a late and more efficient cell death, offering significant advantage (2 orders of magnitude) over photosensitizers that cause unspecific oxidative stress. We are confident that this concept can be used to develop better light-activated drugs. Abbreviations: ΔΨm: mitochondrial transmembrane inner potential; AAU: autophagy arbitrary units; ATG5, autophagy related 5; ATG7: autophagy related 7; BAF: bafilomycin A(1); BSA: bovine serum albumin; CASP3: caspase 3; CF: carboxyfluorescein; CTSB: cathepsin B; CVS: crystal violet staining; DCF: dichlorofluorescein; DCFH(2): 2ʹ,7ʹ-dichlorodihydrofluorescein; DMMB: 1,9-dimethyl methylene blue; ER: endoplasmic reticulum; HaCaT: non-malignant immortal keratinocyte cell line from adult human skin; HP: hydrogen peroxide; LC3B-II: microtubule associated protein 1 light chain 3 beta-II; LMP: lysosomal membrane permeabilization; LTG: LysoTracker™ Green DND-26; LTR: LysoTracker™ Red DND-99; 3-MA: 3-methyladenine; MB: methylene blue; mtDNA: mitochondrial DNA; MitoSOX™: red mitochondrial superoxide probe; MTDR: MitoTracker™ Deep Red FM; MTO: MitoTracker™ Orange CMTMRos; MT-ND1: mitochondrially encoded NADH:ubiquinone oxidoreductase core subunit 1; MTT: methylthiazolyldiphenyl-tetrazolium bromide; (1)O(2): singlet oxygen; OH(.) hydroxil radical; PRKN/parkin: parkin RBR E3 ubiquitin protein ligase; PBS: phosphate-buffered saline; PI: propidium iodide; PDT: photodynamic therapy; PS: photosensitizer; QPCR: gene-specific quantitative PCR-based; Rh123: rhodamine 123; ROS: reactive oxygen species RTN: rotenone; SQSTM1/p62: sequestosome 1; SUVs: small unilamellar vesicles; TBS: Tris-buffered saline

This study consisted of a palynological, microbiological, and physicochemical characterization of fifteen samples of Spanish honey sold under quality brands with different botanical and geographical origins from two consecutive harvest years (2010 and 2011). Eight of the fifteen honey samples were classified as monofloral honey from botanical origins Persea americana, Castanea sativa, Rosmarinus officinalis, Eucalyptus sp., and Thymus sp. With regard to microbiological analyses, mold, and yeast counting, Staphylococcus aureus, Salmonella, sulfite-reducing clostridia, and Escherichia coli were not detected in any of the samples. Aerobic mesophilic microorganisms were detected only in some samples and the counts in these cases were low. Despite the great variability between samples, the results obtained in the physicochemical analysis were consistent with the limits set by the Council Directive 2001/100. Honey samples showed high variability between two consecutive harvests, since, even if they had similar geographical origins they showed different nectar floral origins. Mieles españolas con marca de calidad: un enfoque multivariado de parámetros fisicoquímicos, calidad microbiológica y origen floral Este estudio consistió en la caracterización botánica, microbiológica y fisicoquímica de quince muestras de miel españolas acogidas a marcas de calidad diferenciada de diferentes orígenes botánicos y geográficos y procedentes de dos cosechas consecutivas (años 2010 y 2011). Ocho de las quince muestras de miel estudiadas fueron clasificadas como mieles monoflorales de Persea americana, Castanea sativa, Rosmarinus officinalis, Eucalyptus sp. y Thymus sp. En relación a los análisis microbiológicos los recuentos de mohos y levaduras, Staphylococcus aureus, Salmonella, clostridios sulfito reductores y Escherichia coli no fueron detectados en ninguna de las muestras. Se detectaron microorganismos aerobios mesófilos solo en algunas muestras y en este caso los recuentos fueron bajos. Aunque se detectaron coliformes, estos podrían estar asociados a un origen ambiental. A pesar de la gran variabilidad entre las muestras, los resultados obtenidos en el análisis fisicoquímico se encontraron dentro de los límites establecidos por la Directiva del Consejo 2001/100. Las muestras de miel mostraron una gran variabilidad entre cosechas porque aunque tuvieron un mismo origen geográfico, hubo diferencias en su origen floral. Este estudio consistió en la caracterización botánica, microbiológica y fisicoquímica de quince muestras de miel españolas acogidas a marcas de calidad diferenciada de diferentes orígenes botánicos y geográficos y procedentes de dos cosechas consecutivas (años 2010 y 2011). Ocho de las quince muestras de miel estudiadas fueron clasificadas como mieles monoflorales de Persea americana, Castanea sativa, Rosmarinus officinalis, Eucalyptus sp. y Thymus sp. En relación a los análisis microbiológicos los recuentos de mohos y levaduras, Staphylococcus aureus, Salmonella, clostridios sulfito reductores y Escherichia coli no fueron detectados en ninguna de las muestras. Se detectaron microorganismos aerobios mesófilos solo en algunas muestras y en este caso los recuentos fueron bajos. Aunque se detectaron coliformes, estos podrían estar asociados a un origen ambiental. A pesar de la gran variabilidad entre las muestras, los resultados obtenidos en el análisis fisicoquímico se encontraron dentro de los l ımites establecidos por la Directiva del Consejo 2001/100. Las muestras de miel mostraron una gran variabilidad entre cosechas porque aunque tuvieron un mismo origen geográfico, hubo diferencias en su origen floral. This work was supported by the Consejería de Sanidad. Junta de Castilla y León [GRS 551/A/10]; Patricia Combarros- Fuertes PhD Research was funded by Consejería de Educación. Junta de Castilla y León and Fondo Social Europeo. info:eu-repo/semantics/publishedVersion

This study shows the potential application of a potentiometric electronic tongue coupled with a lab-made DataLogger device for the classification of dairy products according to the type of milk used in their production, i.e., natural, fermented and UHT milk. The electronic tongue device merged a commercial pH electrode and 15 lipid/polymeric membranes, which were obtained by a drop-by-drop technique. The potentiometric signal profiles gathered from the 16 sensors, during the analysis of the 11 dairy products (with ten replicate samples), together with principal component analysis showed that dairy samples could be naturally grouped according to the three types of milk evaluated. To further investigate and verify this capability, a linear discriminant analysis together with a simulated annealing variable selection algorithm was also applied to the electrochemical data, which were randomly split into two datasets, one used for model training and internal-validation using a repeated K-fold cross-validation procedure (with 64\% of the data); and the other for external validation purposes (containing the remaining 36\% of the data). The multivariate supervised strategy used allowed establishing a classification model, based on the potentiometric information of four sensor lipid membranes, which enabled achieving a successful discrimination rate of 100\\% for both internal- and external-validation processes. The demonstrated versatility of the built electronic tongue for discriminating dairy products according to the type of milk used in their production combined with its simplicity, low-cost and fast time analysis may envisage a possible future application in dairy industry., This study was funded in part by the Ministry of Research, Technology and Higher Education, the Republic of Indonesia, Project 001/SP2H/LT/DRPM/IV/2017. The authors also thank the Directorate General of Islamic Education and Instituto Politécnico de Bragança, Portugal, for their support throughout the completion of this work. This work was financially supported by Project POCI01–0145-FEDER-006984 – Associate Laboratory LSRE-LCM, Project UID/BIO/04469/2013 – CEB and strategic project PEst-OE/ AGR/UI0690/2014 – CIMO all funded by FEDER - Fundo Europeu de Desenvolvimento Regional through COMPETE2020 - Programa Operacional Competitividade e Internacionalização (POCI) – and by national funds through FCT - Fundação para a Ciência e a Tecnologia, Portugal., info:eu-repo/semantics/publishedVersion

When making long-term plans for their asset portfolios, decision-makers have to define a priori a maintenance budget that is to be shared among the several assets and managed throughout the planning period. During the planning period, the a priori budget is then allocated by managers to different operation and maintenance interventions ensuring the overall performance of the system. Because asset degradation is stochastic, a considerable amount of uncertainty is associated with this problem. Hence, to define a robust budget, it is essential to account for several degradation scenarios pertaining to the individual condition of each asset. This paper presents a novel mathematical formulation to tackle this problem in a heterogeneous multi-asset portfolio. The proposed mathematical model was formulated as a mixed-integer programming two-stage stochastic optimization model with mean–variance constraints to minimize the number of scenarios with an insufficient budget. A Gamma process was used to model the condition of each individual asset while taking into consideration different technological features and operating conditions. We compared the solutions obtained with our model to alternative practices in a set of generated instances covering different types of multi-asset portfolios. This comparison allowed us to explore the value of modeling uncertainty and how it affects the generated solutions. The proposed approach led to gains in performance of up to 50% depending on the level of uncertainty. Furthermore, the model was validated using real-world data from a utility company working with portfolios of power transformers. The results obtained showed that the company could reduce costs by as much as 40%. Further conclusions showed that the cost-saving potential was higher in asset portfolios in worse condition and that defining a priori operation and maintenance interventions led to worse results. Finally, the results showcased how different decision-maker risk-levels affect the value of taking uncertainty into account.

Negatively charged macromolecules play a starring role in Ca 2 + saturation at interfaces: they act as organized points for biomineral growth in nature. However, the role positively charged interfaces play in biomineralization remains unknown. Therefore, we decided to use a cationic Langmuir-Blodgett (LB) film composed of dioctadecyldimethylammonium bromide (DOMA) and type-I collagen in the presence of CaCl 2 solutions to guide CaCO 3 growth on titanium surfaces. Ca 2 + was able to interact with DOMA monolayers, leading to impressive cation excess at the film surface, as evidenced by the increased positive zeta potential of the LB films. Additionally, molecular dynamics simulations showed that Ca 2 + co-ions were able to accumulate on the positively charged LB interface, especially because configurations like R-N(+)-counterion-Ca 2 + existed therein. Counterion-mediated Ca 2 + accumulation on the surface was mainly driven by Cl − ions, which were much closer to Ca 2 + ions than Br − ions. Ca 2 + excess on the surface was sufficient to grow continuous and particulate CaCO 3 films on titanium surfaces. In addition, collagen presence induced changes in CaCO 3 film morphology and organization. Finally, we were able to confirm that positively charged organic interfaces can act as templates for biomineral growth because counterion-mediated Ca 2 + accumulation on these surfaces can drive subsequent crystal growth. This study provides insight into biomineralization templated by positively charged organic matrixes and into the design of bioinspired coatings for metallic surfaces.

Table olives are prone to the appearance of sensory defects that decrease their quality and in some cases result in olives unsuitable for consumption. The evaluation of the type and intensity of the sensory negative attributes of table olives is recommended by the International Olive Council, although not being legally required for commercialization. However, the accomplishment of this task requires the training and implementation of sensory panels according to strict directives, turning out in a time-consuming and expensive procedure that involves a degree of subjectivity. In this work, an electronic tongue is proposed as a taste sensor device for evaluating the intensity of sensory defects of table olives. The potentiometric signal profiles gathered allowed establishing multiple linear regression models, based on the most informative subsets of signals (from 24 to 29 recorded during the analysis of olive aqueous pastes and brine solutions) selected using a simulated annealing meta-heuristic algorithm. The models enabled the prediction of the median intensities (R2 ≥ 0.942 and RMSE ≤ 0.356, for leave-one-out or repeated K-fold cross-validation procedures) of butyric, musty, putrid, winey-vinegary, and zapateria negative sensations being, in general, the predicted intensities within the range of intensities perceived by the sensory panel. Indeed, based on the predicted mean intensities of the sensory defects, the electrochemical-chemometric approach developed could correctly classify 86.4% of the table olive samples according to their trade category based on a sensory panel evaluation and following the International Olive Council regulations (i.e., extra, 1st choice, 2nd choice, and olives that may not be sold as table olives). So, the satisfactory overall predictions achieved demonstrate that the electronic tongue could be a complementary tool for assessing table olive defects, reducing the effort of trained panelists and minimizing the risk of subjective evaluations., This work was financially supported by Project POCI-01-0145-FEDER-006984—Associate Laboratory LSRE-LCM, by Project UID/QUI/00616/2013 —CQ-VR, and UID/AGR/00690/ 2013—CIMO, all funded by Fundo Europeu de Desenvolvimento Regional (FEDER) through COMPETE2020—Programa Operacional Competitividade e Internacionalização (POCI) and by national funds through Fundação para a Ciência e a Tecnologia (FCT), Portugal. Strategic funding of UID/BIO/04469/2013 unit is also acknowledged. Nuno Rodrigues thanks FCT, POPH-QREN, and FSE for the Ph.D. Grant (SFRH/BD/104038/2014)., info:eu-repo/semantics/publishedVersion

The ELBA coarse-grained force field was originally developed for lipids, and its water model is described as a single-site Lennard-Jones particle with electrostatics modeled by an embedded point-dipole, while other molecules in this force field have a three (or four)-to-one mapping scheme. Here, ELBA was applied to investigate the self-assembly processes of dodecyl-phosphocholine (DPC) micelle, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine/1,2-dihexaoyl-sn-glycero-3-phosphocholine (DPPC/DHPC) bicelles, and DPPC/cyclohexane/water reverse micelles through coarse-grained molecular dynamics (MD) simulations. New parameters were obtained using a simplex algorithm-based calibration procedure to determine the Lennard-Jones parameters for cyclohexane, dodecane, and cyclohexane–dodecane cross-interactions. Density, self-diffusion coefficient, surface tension, and mixture excess volume were found to be in fair agreement with experimental data. These new parameters were used in the simulations, and the obtained struct...

Mead is a traditional beverage that results from the alcoholic fermentation of diluted honey performed by yeasts. Although the process of mead production has been optimized in recent years, studies focused on its sensory properties are still scarce. Therefore, the aim of this work was to analyse the sensory ttributes of mead produced with free or immobilized cells of the Saccharomyces cerevisiae strains QA23 and ICV D47, and to establish potential correlations with its olatile composition. In the volatile composition of mead, the effect of yeast condition was more important than the strain. In respect to sensory analysis, the most pleasant aroma descriptors were correlated with mead obtained with free yeast cells, independently of the strain. Both sensory analysis and volatile composition indicates that the most pleasant mead was produced by free yeast cells. Although this study has provided a significant contribution, further research on the sensory quality of mead is still needed., Portuguese Foundation for Science and Technology (FCT) through a PhD grant (SFRH/BD/45820/2008). This research was partially supported through the PTDC project (PTDC/AGR-ALI/68284/2006) awarded by the FCT. This study was supported by the Portuguese Foundation for Science and Technology (FCT) under the scope of the strategic funding of UID/BIO/04469/2013 unit and COMPETE 2020 (POCI-01-0145-FEDER-006684) and BioTecNorte operation (NORTE-01-0145-FEDER-000004) funded by European Regional Development Fund under the scope of Norte2020 – Programa Operacional Regional do Norte, info:eu-repo/semantics/publishedVersion

Glucose, fructose and sucrose are sugars with known physiological effects, and their consumption has impact on the human health, also having an important effect on food sensory attributes. The analytical methods routinely used for identification and quantification of sugars in foods, like liquid chromatography and visible spectrophotometry have several disadvantages, like longer analysis times, high consumption of chemicals and the need for pretreatments of samples. To overcome these drawbacks, in this work, a potentiometric electronic tongue built with two identical multi-sensor systems of 20 cross-selectivity polymeric sensors, coupled with multivariate calibration with feature selection (a simulated annealing algorithm) was applied to quantify glucose, fructose and sucrose, and the total content of sugars as well. Standard solutions of ternary mixtures of the three sugars were used for multivariate calibration purposes, according to an orthogonal experimental design (multilevel fractional factorial design) with or without ionic background (KCl solution). The quantitative models&rsquo, predictive performance was evaluated by cross-validation with K-folds (internal validation) using selected data for training (selected with the K-means algorithm) and by external validation using test data. Overall, satisfactory predictive quantifications were achieved for all sugars and total sugar content based on subsets comprising 16 or 17 sensors. The test data allowed us to compare models&rsquo, predictions values and the respective sugar experimental values, showing slopes varying between 0.95 and 1.03, intercept values statistically equal to zero (p-value &ge, 0.05) and determination coefficients equal to or greater than 0.986. No significant differences were found between the predictive performances for the quantification of sugars using synthetic solutions with or without KCl (1 mol L&minus, 1), although the adjustment of the ionic background allowed a better homogenization of the solution&rsquo, s matrix and probably contributed to an enhanced confidence in the analytical work across all of the calibration working range.

The USFDA has approved pramlintide, commercially named Symlin (sIAPP), as adjunctive therapy for type 2 diabetes (T2D). This analogue of the human amylin peptide (hIAPP) has triple proline substitutions typical of the rat isoform (rIAPP). Recently, it was proposed that pramlintide solubility and aggregation resistance might be improved by incorporating further mutations, as S20R, screened from the wild-type porcine isoform (pIAPP), which leads to the variant named sIAPP+. To better elucidate how such properties might be systematically induced in rationally designed analogues, we performed comparative assessments of rIAPP, sIAPP, and sIAPP+ using replica-exchange molecular dynamics (REMD) with an accurate combination of force field Charmm22* and explicit aqueous solvation TIP4P/Ew. Our thermo-structural analyses show that sIAPP exhibits a thermal conversion channel of helices[Formula: see text]-sheets resembling hIAPP. This channel is depleted in rIAPP and is absent in sIAPP+. As a consequence, sIAPP+ presents an overall decrease of β-like secondary structures and an overstabilization of α-helices. Additionally, we observed in rIAPP and sIAPP+ an increase in the backbone RMSF of molecular terminals and the exposed area of key residues. These structural features of sIAPP+ suggest a nonamyloidogenic character, which is corroborated by our judicious estimate of the electrostatic component of the solvation free energy using a generalized Born model, and so it may constitute an alternative strategy to sIAPP as a peptide analogue of hIAPP. Furthermore, our findings confirm that different aggregation propensities of amylin and its analogues are synergistically modulated by long-range effects of key mutations. Graphical Abstract S20R-Pramlintide.

A chiral derivatizing agent (CDA) with the aldehyde function has been widely used in discriminating chiral amines because of the easy formation of imines under mild conditions. There is a preference for the use of cyclic aldehydes as a CDA since their lower conformational flexibility favors the differentiation of the diastereoisomeric derivatives. In this study, the imines obtained from the reaction between (S)-citronellal and the chiral amines (sec-butylamine, methylbenzylamine, and amphetamine) were analyzed by the nuclear Overhauser effect (NOE). Through NOE, it was possible to observe that the ends of the molecules were close, suggesting a quasi-folded conformation. This conformation was confirmed by theoretical calculations that indicated the London forces and the molecular orbitals as main justifications for this conformation. This conformational locking explains the good separation of 13C NMR signals between the diastereomeric imines obtained and, consequently, a good determination of the enantiomeric excess using the open chain (S)-citronellal as a CDA.

An electronic nose, comprising nine metal oxide sensors, has been built aiming to classify olive oils according to the fruity intensity commercial grade (ripely fruity or light, medium and intense greenly fruity), following European regulated complementary terminology. The lab-made sensor device was capable to differentiate standard aqueous solutions (acetic acid, cis-3-hexenyl, cis-3-hexen-1-ol, hexanal, 1-hexenol and nonanal) that mimicked positive sensations (e.g., fatty, floral, fruit, grass, green and green leaves attributes) and negative attributes (e.g., sour and vinegary defects), as well as to semi-quantitatively classify them according to the concentration ranges (0.05 to 2.25 mg/kg). For that, unsupervised (principal component analysis) and supervised (linear discriminant analysis: sensitivity of 92% for leave-one-out cross validation) classification multivariate models were established based on nine or six gas sensors, respectively. It was also showed that the built E-nose allowed differentiating/discriminating (sensitivity of 81% for leave-one-out cross validation) extra virgin olive oils according to the perceived intensity of fruitiness as ripely fruity, light, medium or intense greenly fruity. In conclusion, the gas sensor device could be used as a practical preliminary non-destructive tool for guaranteeing the correctness of olive oil fruitiness intensity labelling., The authors are grateful to the Foundation for Science and Technology (FCT, Portugal) for financial support by national funds FCT/ MCTES to CIMO (UIDB/00690/2020), to CEB (UIDB/04469/2020) and to BioTecNorte operation (NORTE-01-0145-FEDER-000004) and Project “GreenHealth - Digital strategies in biological assets to improve wellbeing and promote green health” (Norte-01-0145-FEDER-000042) funded by the European Regional Development Fund (ERDF) under the scope of Regional Operational Program North 2020. ´Itala Marx acknowledges the Ph.D. research grant (SFRH/BD/137283/2018) provided by FCT. Nuno Rodrigues thanks the National funding by FCTFoundation for Science and Technology, P.I., through the Institutional Scientific Employment Program-contract., info:eu-repo/semantics/publishedVersion

The properties of ionic micelles depend on the nature of the counterion, and these effects become more evident as the ion adsorption at the interface increases. Prediction of the relative extent of ion adsorption is required for rational design of ionic micellar aggregates. Unlike the well understood adsorption of monatomic ions, the adsorption of polyatomic ions is not easily predicted. We combined experimental and computational methods to evaluate the affinity of hydrotropic ions, i.e., ions with polar and apolar regions, to the surface of positively charged micelles. We analyzed cationic micelles of dodecyltrimethylammonium and six hydrotropic counterions: methanesulfonate, trifluoromethanesulfonate, benzenesulfonate, acetate, trifluoroacetate and benzoate. Our results demonstrated that the apolar region of hydrotropic ions had the largest influence on micellar properties. The dehydration of the apolar region of hydrotropic ions upon their adsorption at the micellar interface determined the ion adsorption extension, differently to what was expected based on Collins' law of matching affinities. These results may lead to more general models to describe the adsorption of ions, including polyatomic ions, at the micellar interface.

The nanoscale pH gradients from a charged membrane interface to the bulk solution, determine fundamental properties of chemical and biological systems. We estimated the proton distribution on micelle surfaces experimentally measuring the apparent pKa of a weak acid linked at varying distances to a micelle anchoring moiety and relating these values to the electrical potential at the micellar surface. The pH probes consisted of benzoic acid connected to chains with variable number (1–5) oxyethylene (−OCH2CH2–) units. The methylene of the terminal oxyethylene was connected to a quaternary nitrogen containing a long hydrocarbon chain. We calculated the apparent pKa (pKap) of the benzoic acid derivatives with surfactant micelles by UV spectroscopy. The difference between the pKa in solution and the pKap in micelles (ΔpK) of all probes was very similar with negatively charged sodium dodecyl sulphate (SDS) or zwitterionic N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS) micelles, indicating that the dissociation of the substituted benzoates occurred at the micellar interface in both SDS and HPS. In contrast, the ΔpK of the probes decreased as a function of the benzoate's distance to the micelle interface in hexadecyltrimethylammonium chloride (CTAC) micelles, The variation of ΔpK with distance, from the CTAC micellar interface to bulk solution, was quantitatively correlated to H+ distribution from the interface. The experimental results coincided with independently calculated Poisson Boltzmann H+ distribution. These results demonstrate that that it is possible to experimentally map H+ gradients from a charged interface.

Producción Científica, A bio-electronic tongue has been developed to evaluate the phenolic content of grape residues (seeds and skins) in a fast and easy way with industrial use in mind. A voltammetric electronic tongue has been designed based on carbon resin electrodes modified with tyrosinase combined with electron mediators. The presence of the phenoloxydase promotes the selectivity and specificity towards phenols. The results of multivariate analysis allowed discriminating seeds and skins according to their polyphenolic content. Partial least squares (PLS) has been used to establish regression models with parameters related to phenolic content measured by spectroscopic methods i.e., total poliphenol content (TPC) and Folin–Ciocalteu (FC) indexes. It has been shown that electronic tongue can be successfully used to predict parameters of interest with high correlation coefficients (higher than 0.99 in both calibration and prediction) and low residual errors. These values can even be improved using genetic algorithms for multivalent analysis. In this way, a fast and simple tool is available for the evaluation of these values. This advantage may be due to the fact that the electrochemical signals are directly related to the phenolic content., Ministerio de Ciencia Innovación y Universidades-FEDER (grants RTI2018-097990-B-100 and BES-2016-077825), Junta de Castilla y León-FEDER (grant VA275P18) y (Infraestructuras Red de Castilla y León (INFRARROJOS) UVA01)

Olive oil is highly appreciated due to its nutritional and organoleptic characteristics. However, a huge compositional variation is observed between olive oils, requiring the use of diverse analytical techniques for its classification including titration, spectrophotometry and chromatography, as well as sensory analysis. Chemical analysis is usually time-consuming, expensive and require skilled technicians, while the sensorial ones are dependent upon individual subjective evaluations, even if performed by trained panellists. This work evaluated and demonstrated the feasibility of using a potentiometric electronic tongue, comprising non-specific lipid polymeric and cross-sensitive sensor membranes, coupled with chemometric tools based on different sub-sets of sensors (from 11 to 14 sensors), to predict key quality parameters of olive oils based on single-run assays. The multivariate linear models established for 23 centenarian olive trees from different cultivars allowed predicting peroxide value, oxidative stability, total phenols and tocopherols contents, CIELAB scale parameters (L*, a* and b* values), as well as 11 gustatory-retronasal positive attributes (green, sweet, bitter, pungent, tomato and tomato leaves, apple, banana, cabbage, fresh herbs and dry fruits) with satisfactory accuracy (0.90±0.07 R2 0.98±0.02 for the repeated K-fold-CV procedure, which ensured that 25% of the data was used for internal-validation purposes). The electronic tongue device had an accuracy statistically similar to that achieved with standard analytical techniques, pointing out the versatility of the device for the fast and simultaneous chemical and sensory analysis of olive oil., Project POCI-01-0145-FEDER-006984 – Associate Laboratory LSRE-LCM, Project UID/BIO/04469/2013 – CEB, Project UID/QUI/50006/2013 - REQUIMTE-LAQV and strategic project PEst-OE/AGR/UI0690/2014 – CIMO all funded by European Regional Development Fund (ERDF) through COMPETE2020 – Programa Operacional Competitividade e Internacionalização (POCI) – and by national funds through FCT – Fundação para a Ciência e a Tecnologia I.P., info:eu-repo/semantics/publishedVersion

Myclobutanil is a chiral triazole fungicide that is employed worldwide. Although enantiomers have the same physical-chemical properties, they may differ in terms of activity, metabolism, and toxicity. This investigation consisted of in vitro enantioselective metabolism studies that employed a human model to assess the risks of myclobutanil in humans. A LC-MS/MS enantioselective method was developed and validated. The enzymatic kinetic parameters (VMAX, KMapp, and CLINT) determined for in vitro rac-myclobutanil and S-(+)-myclobutanil metabolism revealed enantioselective differences. Furthermore, human CYP450 enzymes did not metabolize R-(-)-myclobutanil. The predicted in vivo toxicokinetic parameters indicated that S-(+)-myclobutanil may be preferentially eliminated by the liver and suffer the first-pass metabolism effect. However, because CYP450 did not metabolize R-(-)-myclobutanil, this enantiomer could reach the systemic circulation and stay longer in the human body, potentially causing toxic effects. The CYP450 isoforms CYP2C19 and CYP3A4 were involved in rac-myclobutanil and S-(+)-myclobutanil metabolism. Although there were differences in the metabolism of the myclobutanil enantiomers, in vitro inhibition studies did not show significant enantioselective differences. Overall, the present investigation suggested that myclobutanil moderately inhibits CYP2D6 and CYP2C9 in vitro and strongly inhibits CYP3A and CYP2C19 in vitro. These results provide useful scientific information for myclobutanil risk assessment in humans.

This study assessed 16 different honey samples in order to select the best one for therapeutic purposes. First, a study of honey's main bioactive compounds was carried out. Then phenolic profiles were determined and specific compounds quantified using a HPLC system coupled to a mass spectrometer. Then, antioxidant activity, by three in vitro methods, and antibacterial activity against reference strains and clinical isolates were evaluated. Great variability among samples was observed regarding ascorbic acid (between 0.34 ± 0.00 and 75.8 ± 0.41 mg/100 g honey; p < 0.001), total phenolic compounds (between 23.1 ± 0.83 and 158 ± 5.37 mg/100 g honey; p < 0.001), and total flavonoid contents (between 1.65 ± 0.11 and 5.93 ± 0.21 mg/100 g honey; p < 0.001). Forty-nine different phenolic compounds were detected, but only 46 of them were quantified by HPLC. The concentration of phenolic compounds and the phenolic profiles varied widely among samples (between 1.06 ± 0.04 and 18.6 ± 0.73 mg/100 g honey; p < 0.001). Antioxidant activity also varied significantly among the samples. All honey varieties exhibited antibacterial activity against both reference and clinical strains (effective concentrations ranged between 0.05 and 0.40 g/mL depending on the honey sample and bacteria tested). Overall, samples with better combinations of bioactive properties were avocado and chestnut honeys. This work was supported by the ConsejeriaFundinǵ de Sanidad of Junta de Castilla y Leoń (Spain); under grant GRS 551/A/10. P.C.-F. was funded by the Consejeriá de Educacioń of Junta de Castilla y Leoń and European Social Fund. Notes The authors declare no competing financial interest. info:eu-repo/semantics/publishedVersion