New chemistry of diazafulvenium methides: one way to pyrazoles

Diazafulvenium methides generated from the solution pyrolysis of pyrazolo[1,5-c][1,3]thiazole-2,2-dioxides participate in [8[pi]+2[pi]] cycloadditions giving pyrazolo[1,5-a]pyridine derivatives. 1-Methyl-diazafulvenium, generated under flash vacuum pyrolysis reaction conditions, undergoes an intramolecular sigmatropic [1,8]H shift giving 1-vinyl-1H-pyrazoles.http://www.sciencedirect.com/science/article/B6THS-4HR7298-7/1/af0dd8d679e7977f53bc0d4af9a5b68

Prediction of friction degradation in highways with linear mixed models

The development of a linear mixed model to describe the degradation of friction on flexible road pavements to be included in pavement management systems is the aim of this study. It also aims at showing that, at the network level, factors such as temperature, rainfall, hypsometry, type of layer, and geometric alignment features may influence the degradation of friction throughout time. A dataset from six districts of Portugal with 7204 sections was made available by the Ascendi Concession highway network. Linear mixed models with random effects in the intercept were developed for the two-level and three-level datasets involving time, section and district. While the three-level models are region-specific, the two-level models offer the possibility to be adopted to other areas. For both levels, two approaches were made: One integrating into the model only the variables inherent to traffic and climate conditions and the other including also the factors intrinsic to the highway characteristics. The prediction accuracy of the model was improved when the variables hypsometry, geometrical features, and type of layer were considered. Therefore, accurate predictions for friction evolution throughout time are available to assist the network manager to optimize the overall level of road safety.This research was funded by FCT—Fundação para a Ciência e Tecnologia (Foundation for Science and Technology), Grants No. UIDB/04029/2020 and UIDB/00319/2020

A shifted hyperbolic augmented Lagrangian-based artificial fish two swarm algorithm with guaranteed convergence for constrained global optimization

This article presents a shifted hyperbolic penalty function and proposes an augmented Lagrangian-based algorithm for non-convex constrained global optimization problems. Convergence to an ε-global minimizer is proved. At each iteration k, the algorithm requires the ε(k)-global minimization of a bound constrained optimization subproblem, where ε(k) → ε. The subproblems are solved by a stochastic population-based metaheuristic that relies on the artificial fish swarm paradigm and a two-swarm strategy. To enhance the speed of convergence, the algorithm invokes the Nelder–Mead local search with a dynamically defined probability. Numerical experiments with benchmark functions and engineering design problems are presented. The results show that the proposed shifted hyperbolic augmented Lagrangian compares favorably with other deterministic and stochastic penalty-based methods.This work was supported by COMPETE [POCI-01-0145-FEDER-007043]; FCT-Fundacao para a Ciencia e Tecnologia within the Project Scope [UID/CEC/00319/2013]; and partially supported by CMAT-Centre of Mathematics of the University of Minho

Caracterização fenotípica e genética de cepas de Bordetella pertussis isoladas em São Paulo, Brasil, 1988-2002

Whooping cough or pertussis was a major cause of childhood morbidity and mortality in the world until the introduction of a whole-cell vaccine in the 1940's. However, since the early 1980's whooping cough cases have increased in many countries, becoming an important problem of public health. This increase may be due to accuracy of laboratory diagnosis and reporting of the disease, a decline in immunity over time, demographic changes, and adaptation of the bacterial population to vaccine-induced immunity. The purpose of this study was to analyze phenotypically and genotypically a collection of 67 Bordetella pertussis isolates recovered during the period 1988-2002 in São Paulo State, Brazil to determine their characteristics and relatedness. All isolates were submitted to susceptibility testing to erythromycin, serotyping, and 56 isolates were analyzed by Pulsed Field Gel Electrophoresis (PFGE). All isolates were susceptible to erythromycin and the majority of them belonged to serotype 1,3. The 56 isolates were classified into 11 PFGE profiles according to the differences in banding patterns. Although more than 60% of the isolates were recovered from patients aged less than three months, almost 15% of them were isolated from adolescents/adults evidencing the increase in the incidence of pertussis among this group of age.A coqueluche ou pertussis foi a maior causa de morbidade e mortalidade infantil em todo o mundo até a introdução de uma vacina na década de 1940. Entretanto, desde a década de 1980, a coqueluche tornou-se, em muitos países , um importante problema de saúde pública. Este acontecimento pode ser atribuído à melhoria do diagnóstico laboratorial e da notificação da doença, declínio da imunidade no decorrer do tempo, mudanças demográficas ou adaptação da população bacteriana à imunidade induzida pela vacina. O objetivo deste estudo foi analisar as características fenotípicas e genotípicas de uma coleção de 67 cepas de Bordetella pertussis isoladas no período 1988-2002 em São Paulo, Brasil. Todas as cepas foram submetidas à determinação do perfil de resistência à eritromicina, à sorotipagem e 56 cepas à eletroforese em campo pulsado (PFGE). Todas as cepas foram sensíveis à eritromicina e a maioria delas pertencia ao sorotipo 1,3. As 56 cepas foram classificadas em 11 perfis de PFGE com base nas diferenças no padrão de bandas. Embora mais de 60% das cepas tenham sido isoladas de crianças com menos de três meses de idade, cerca de 15% delas era de adolescentes/adultos evidenciando um aumento da incidência da coqueluche nesse grupo etário

Effect of the acid environment on the electrochemical behaviour of 1045 steel reinforced cement

External corrosion is one of the most common causes of oilwell casing failure. Hostile environments can be due to acidizing treatments. Although it is common to add corrosion inhibitors and oxygen scavengers in acidic solutions to control external casing corrosion, their real efficiency is unknown yet. Therefore, it is important to establish how aggressive to steel are the different hostile environments to help decide which acidic systems can be used. A comparative evaluation of the corrosion of steel immersed in hardened cement slurries submitted to commonly acidizing agents is suggested. The performance of Special Class Portland Cement Slurries reinforced with polished SAE 1045 steel was evaluated by electrochemical measurements as a function of time. Open circuit potential, polarization curves and electrochemical impedance spectroscopy were studied. 15.0 wt% HCl, 12.0 wt% HCl + 3.0 wt% HF (regular mud acid), 10.0 wt% HAc + 1.5 wt% HF and a simulated hardened cement slurry pore solution were used as electrolytes. The most aggressive acid solution to plain Portland hardened cement slurries was the regular mud acid. 10.0 wt% HAc + 1.5 wt% HF electrolytes were the least aggressive ones, showing open circuit potentials around +250 mV compared to -130 mV of the simulated hardened cement slurry pore solution after the first 24 hours of immersion. This behavior was observed during two months at least. Similar corrosion rates were shown between both electrolytes, around 0.01 μA.cm-2. Total impedance values, insipient arcs and large polarization resistance capacitive arcs on the Nyquist plots, indicating passivity process, confirmed the behaviour of the system in the 10.0 wt% HAc + 1.5 wt% HF electrolyte.The authors acknowledge FACEPE and PRH30/ANP/MCTPETROBRAS for the financial support

Adsorption equilibrium of fructose, glucose and sucrose for cationic resins in the sodium and potassium form

Separation of glucose from mixtures of fructose and sucrose in molasses is a major challenge in industrial sugar chromatographic separations. The efficiency of a chromatographic process is largely dependent on the adsorbent used. Sulfonated poly(styrene-co-divinylbenzene) (PS-DVB) ion exchange resins are the most frequently used for sugars separation, generally in a cationic form. The cation will complex with the hydroxyl group of the sugar leading to a selective adsorption according to the orientation of the hydroxyl group. Thus, the conformation of the sugar determines its relative affinity for the resin and its distribution coefficient. Consequently, fructose forms the more stable sugar-cation complex being preferentially adsorbed in the resin followed by glucose. Sucrose interacts very weakly with the cation and is partially or totally excluded from the resin matrix owing to its larger molecular size. The separation process is usually carried out at high temperatures. However, this implies high energy costs and an elevated level of hydrolysis. Adsorption isotherms of the sugars present in a mixture are a very important parameter for the selection of the adsorbent to be used in the chromatographic separation. Therefore, in this study, the adsorption isotherms of glucose, fructose and sucrose were determined for two resins of PS-DVB in the sodium and potassium forms. Potassium and sodium are the most recommended cations for the separation of sucrose, fructose and glucose. The sodium and potassium resins matrix used in this work consist in meshes of 500-600 μm and 290-350 μm, respectively. Solutions with single and multi-component mixtures of the three sugars were used at 25ºC and 40ºC. A static method was used to determine the equilibrium adsorptions: 3.5 mL of solutions with different sugar concentrations were added to a known amount of adsorvent. The mixture was held for 8h under agitation and a fixed temperature and a final concentration in equilibrium with resin was determined by HPLC. As expected, the results achieved showed that for all the conditions, fructose is the most adsorved sugar followed by glucose and sucrose. For both resins, the increase of temperature conducted to a decrease on the adsorption constant for all the sugars in the mono-component mixtures. Nevertheless, the adsorption in multi-component mixtures was not significantly affected by the temperature in the sodium resin, and regarding the potassium resin only a small increase in the adsorption was observed. Multi-component mixtures at 25 ºC showed a decrease in the adsorption as compared with mono-component mixtures. However, at 40ºC the adsorption observed for the multi-component mixtures was higher than the observed for the mono-component ones. The sugars that demonstrated lower selectivity values were fructose/glucose since these sugars have the same molecular weight. Sucrose/fructose selectivity showed a higher value when compared with sucrose/glucose because of the complex formed between fructose and the resin. This profile was found for both resins used, regardless of temperature. Selectivity of both resins decreased with the increase of the temperature values. Nevertheless, the selectivity obtained for the potassium resin was higher as compared to the selectivity obtained for the sodium resin. In sum, potassium resin appears to be the most suitable adsorvent and an operational temperature of 25 ºC showed the best results

Dietary natural plant extracts can promote growth and modulate oxidative status of Senegalese Sole Postlarvae under standard/challenge conditions

Plant extracts are known for their high content and diversity of polyphenols, which can improve fish oxidative status. A growth trial with Senegalese sole postlarvae (45 days after hatching) fed with one of four experimental diets—control (CTRL), and supplemented with curcumin (CC), green tea (GT), and grape seed (GS) extracts—was performed to assess if supplementation could improve growth performance and oxidative status. At the end of the growth trial, postlarvae were submitted to a thermal stress to assess their robustness. Sole growth was improved by CC and GS diets when compared to those fed the CTRL. CC and CTRL postlarvae presented the lowest oxidative damage (lipid peroxidation and protein carbonylation values). Stress-related biomarkers (heat shock protein 70 and glutathione-S-transferase) decreased in CC fish compared to those fed the CTRL diet, which might be due to a direct antioxidant capacity. In contrast, oxidative damage increased in GT and GS sole reared in standard conditions. However, after a thermal stress, GT and GS diets prevented the increase of protein carbonylation content and the decrease of antioxidant glutathione, depending on exposure time. Overall, dietary supplementation with natural extracts modulated oxidative status and stress response after a short/long-term exposure to temperature.UIDB/04326/2020, IF/00482/2014/CP1217/CT0005, CEECIND/00425/2017, RTA2017-00054-C03-01info:eu-repo/semantics/publishedVersio

Characterization of Soybean Cultivars for Biodiesel Production

Due to environmental issues involving the polluting gasesemission, Brazil has adopted the policy of using oil and biodiesel. For biodiesel production, the main raw material used in Brazil is soybean oil. The development of the numerous genotypes of this culture has always considered quantitative aspects. The objective was to qualitatively characterize 12 soybean cultivars for biodiesel production. The experimental design was randomized blocks with three replicates. The cultivars were sown in December 2016, in no-tillage system, in Ponta Grossa, Paraná, Brazil (-25.093056, -50.063327 UTM). The analyzed variables were: oil and protein contents, acidity index and specific mass. It was concluded that there were no significant differences among the cultivars for oil and protein contents. For the variables acidity index and specific mass, there were significant differences among the cultivars, being below the limits established by the Brazilian legislation for vegetable oil, but with potential for biodiesel production

Coaxial fibres incorporated with phase change materials for thermoregulation applications

Nowadays, the growing concern about improving thermal comfort in different structures (textiles, buildings, and pavements, among others) has stimulated research into phase change materials (PCMs). The direct incorporation of PCMs into composite materials can cause mechanical impacts. Therefore, this study focuses on the design of phase change coaxial fibres (PCFs), using commercial cellulose acetate (CA) or recycled CA obtained from cotton fabrics (CAt) as the sheath and polyethylene glycol (PEG) 2000 as the core, via the wet spinning method; the fibres vary in molecular weight, concentration and ejection velocity. The fibres were assessed for their optical, chemical, thermal, and mechanical properties. The presence of PEG2000 is confirmed in the core of the fibres. Thermal analyses revealed a mass loss at high temperatures, attributable to the presence of PEG2000. Notably, the fibres with CA (Mn 30,000) showed superior thermal and mechanical performance. The melting point of PEG2000 incorporated into these PCFs coincided with the melting point of pure PEG2000 (about 55 °C), with a slight deviation, indicating that PCFs were obtained. Finally, the results point to the application of the fibres in civil engineering materials requiring a phase change between 50 and 60 °C, providing promising prospects for their use in applications requiring thermoregulatory properties.This research was funded by the Portuguese Foundation for Science and Technology (FCT) under the projects MicroCoolPav EXPL/EQUEQU/1110/2021 and NanoAir PTDC/FISMAC/6606/2020 (https://doi.org/10.54499/PTDC/FIS-MAC/6606/2020) and within the framework of Strategic Funding UIDB/04650/2020, UIDB/04029/2020 (https://doi.org/10.54499/UIDB/04029/2020) and UID/QUI/0686/2020. I.R.S. and H.P.F. would like to thank FCT for their funding contracts 2022.00763.CEECIND (https://doi.org/10.54499/2022.00763.CEECIND/CP1718/CT0006) and 2021.02720.CEECIND (https://doi.org/10.54499/DL57/2016/CP1377/CT0098)