Oleic acid esterification catalyzed by zeolite y - model of the biomass conversion

Lignocellulosic biomass is a promising renewable source for production of fuels and chemicals with significant life cycle and economy of scale advantages over other biomass sources, such as starches, vegetable oils, and animal fats. The large-scale application of zeolites in biomass conversion can be explained by with adjustable confinement at the nano scale, Brønsted acid strength that derive from its Si/Al ratio and high thermal stability1. In this context, the aim of this study was to test the catalytic activity of zeolite H-Y with high Si/Al ratio for its application in the esterification reaction of oleic acid (OA) with methanol (MeOH) for the synthesis of alkyl esters. Zeolite Y in protonated form with Si / Al = 80 ratio was obtained from Zeolyst International. The catalytic activity of zeolite H-Y was carried out using the esterification reaction of OA by MeOH. The experiments were conducted in reflux system with magnetic stirring at different temperatures (60 and 75 °C), catalyst contents (10 %), OA mass ratios (1:2, 1:3 and 1:6) and residence times (0.5, 1, 1.5, 2, 3, 4.5, 6, 8, 12 and 16 hs). The reaction mixture was collected from the reflux system, and cooled to room temperature. The solution was removed from the catalyst by filtration. The conversion was defined as the change of acid content before and after the oil reaction by the acid content of the initial oil. An interpretation of the catalytic activity is given from theoretical calculations.Analysis indicate that the increase in reaction time results in higher ester conversion rates, reaching the reaction equilibrium after 16 hs of reaction, according to Kirumakki et. al. the time required to achieve equilibrium depends on the reactants used2. It is observed that the conversion of OA results in a high reaction time when is compared to previous works2-4, the main effect for this system is centered in the high Si/Al ratio, which results in the less presence of active sites available in the catalytic process. The optimum reaction conditions were obtained with a molar ratio of 1:3 and 75 °C, resulting in 82 % conversion of ester after 16 hs of reaction. The higher alcohol concentration in the system shifts the equilibrium of the reaction towards the formation of products, as well as the decrease in the viscosity of the reactional system, reducing the transfer rate, which results in a high conversion when compared to the others catalytic tests. According to our previous work, the esterification of carboxylic acids presents a competitive adsorption between methanol and carboxylic acid on the Brønsted acid site5, so that the main hypothesis for the lower product conversion in the esterification reaction with 1:6 molar ratio is related to the adsorption of MeOH on the active site. The effect of self-catalysis on the reactional environment is not reported in the studies cited, according to Raia et. al., auto-catalysis in esterification has a significant importance in the conversion of free fatty acids6. The uncatalyzed reaction resulted in approximately 16 % conversion after 16 hs of reaction, and this result serves as a comparison for the conditions in which the catalyst is added to the system. The H-Y catalyst proved to be efficient and promising for the esterification of OA with MeOH, however, it presented a high reaction time can be optimized with the increase of temperature and greater mass of catalyst, thus, further studies are needed to describe the reaction mechanisms in order to understand the conversion of biomass on the surface of acid zeolites.Fil: Gomes, Glaucio José. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Química. Laboratorio de Estructura Molecular y Propiedades; Argentina. Universidade Estadual de Maringá. Departamento de Engenharia Química.; BrasilFil: Dal Pozzo, Daniel M.. Universidade Federal do Paraná; BrasilFil: Zalazar, Maria Fernanda. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; ArgentinaFil: Costa, M. B.. Universidade Federal do Paraná; BrasilFil: Arroyo, Pedro Augusto. Universidade Estadual de Maringá. Departamento de Engenharia Química.; BrasilFil: Bittencourt, Paulo R. S.. Universidade Federal do Paraná; BrasilVI San Luis School and Conference on Surfaces, Interfaces and CatalysisSanta FeArgentinaInstituto de Investigaciones en Catálisis y PetroquímicaUniversidad Nacional del Litora

Oleic Acid Esterification Catalyzed By Zeolite Y-Model of the Biomass Conversion

Residual oils and fats are promising renewable sources for the production of liquid fuels and the synthesis of various chemicals with significant life cycle and large-scale economic advantages over other biomass sources. Thus, oleic acid esterification was investigated on zeolites type FAU and sulfuric acid by kinetic, spectroscopic assessments and theoretical calculations using a hybrid ONIOM scheme. In the catalytic tests, the solid catalyst with the highest Si/Al (H-Y-80) ratio showed the highest catalytic activity for esterification (92% conversion) as compared to H-Y-5.2 (66% conversion), Na-Y (15% conversion) and homogeneous acid catalysis (89% conversion). The catalytic activity between different acid catalysts is discussed. It was observed that the acidity of the active sites and the hydrophobicity resulting from the Si/Al molar ratio influence the esterification conversion. Theoretical calcultations predicts that the voluminous confined space of the FAU zeolite perfectly accommodates the oleic acid molecule in the adsorption step (Eads= -25.5 kJ mol-1) and the van der Waals interactions of the zeolite walls with the aliphatic chain help to accommodate the bulky molecule between the supercages. Experimental and theoretical results confirm that H-Y-80 zeolite applied in the esterification reaction can be an efficient catalyst in processes involving conversion of unsaturated fatty acids.Fil: Gomes, Glaucio José. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; ArgentinaFil: Dal Pozzo, Daniel M.. Universidade Federal do Paraná; BrasilFil: Zalazar, Maria Fernanda. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; ArgentinaFil: Budke Costa, Michelle. Universidade Federal do Paraná; BrasilFil: Arroyo, Pedro Augusto. Universidade Estadual de Maringá; BrasilFil: Bittencourt, Paulo R. S.. Universidade Federal do Paraná; Brasi

Using shared needles for subcutaneous inoculation can transmit bluetongue virus mechanically between ruminant hosts

Bluetongue virus (BTV) is an economically important arbovirus of ruminants that is transmitted by Culicoides spp. biting midges. BTV infection of ruminants results in a high viraemia, suggesting that repeated sharing of needles between animals could result in its iatrogenic transmission. Studies defining the risk of iatrogenic transmission of blood-borne pathogens by less invasive routes, such as subcutaneous or intradermal inoculations are rare, even though the sharing of needles is common practice for these inoculation routes in the veterinary sector. Here we demonstrate that BTV can be transmitted by needle sharing during subcutaneous inoculation, despite the absence of visible blood contamination of the needles. The incubation period, measured from sharing of needles, to detection of BTV in the recipient sheep or cattle, was substantially longer than has previously been reported after experimental infection of ruminants by either direct inoculation of virus, or through blood feeding by infected Culicoides. Although such mechanical transmission is most likely rare under field condition, these results are likely to influence future advice given in relation to sharing needles during veterinary vaccination campaigns and will also be of interest for the public health sector considering the risk of pathogen transmission during subcutaneous inoculations with re-used needles

Reliability and inter-observer agreement of dermoscopic diagnosis of melanoma and melanocytic naevi

The aim of this study was to analyse the reliability and the inter- observer agreement of dermoscopy in the diagnosis of melanocytic skin lesions. Nine dermatologists, with a different training experience and who routinely used dermoscopy in different hospitals in Italy, evaluated clinical and dermoscopy photographs of 15 melanocytic lesions (four invasive melanomas, four histologically common naevi, and seven naevi with histological atypia). A further series of dermoscopic photographs of 40 melanocytic lesions was evaluated to quantify inter-observer concordance in recognizing dermoscopic criteria. Compared to the true (histological) diagnosis, clinical diagnosis (categories: melanoma, common naevus, atypical naevus) was correct in 40% of cases (range, 27-53%). The percentage raised to 55% (40-73%) by the use of dermoscopy, with an average improvement of 15.6%. Concerning melanoma, clinical diagnosis resulted in a sensitivity of 41.9%, specificity of 77.8%, positive predictive value (PPV) of 36.1%, negative predictive value (NPV) of 81.8%. By using dermoscopy, an improvement of diagnostic performance was found (sensitivity 75%, specificity 88.8%, VPP 71.0%, VPN 90.7%). The inter-observer agreement in melanoma diagnosis, by using dermoscopy, was similar to that obtained by clinical examination (k statistics = 0.54 and 0.52, respectively). Concerning dermoscopic criteria, the best agreement among observers was found for pseudopods, a dermoscopic parameter related to the radial growth phase of melanoma. We conclude that dermoscopy is an useful tool for a non-invasive diagnosis of melanocytic skin lesions, improving the diagnostic performance compared to clinical examination

Efficacy, Stability, and Safety Evaluation of New Polyphenolic Xanthones Towards Identification of Bioactive Compounds to Fight Skin Photoaging

Antioxidants have long been used in the cosmetic industry to prevent skin photoaging, which is mediated by oxidative stress, making the search for new antioxidant compounds highly desirable in this field. Naturally occurring xanthones are polyphenolic compounds that can be found in microorganisms, fungi, lichens, and some higher plants. This class of polyphenols has a privileged scaffold that grants them several biological activities. We have previously identified simple oxygenated xanthones as promising antioxidants and disclosed as hit, 1,2-dihydroxyxanthone (1). Herein, we synthesized and studied the potential of xanthones with different polyoxygenated patterns as skin antiphotoaging ingredients. In the DPPH antioxidant assay, two newly synthesized derivatives showed IC₅₀ values in the same range as ascorbic acid. The synthesized xanthones were discovered to be excellent tyrosinase inhibitors and weak to moderate collagenase and elastase inhibitors but no activity was revealed against hyaluronidase. Their metal-chelating effect (FeCl₃ and CuCl₂) as well as their stability at different pH values were characterized to understand their potential to be used as future cosmetic active agents. Among the synthesized polyoxygenated xanthones, 1,2-dihydroxyxanthone (1) was reinforced as the most promising, exhibiting a dual ability to protect the skin against UV damage by combining antioxidant/metal-chelating properties with UV-filter capacity and revealed to be more stable in the pH range that is close to the pH of the skin. Lastly, the phototoxicity of 1,2-dihydroxyxanthone (1) was evaluated in a human keratinocyte cell line and no phototoxicity was observed in the concentration range tested.This research was supported by national funds through FCT, Foundation for Science and Technology, within the scope of UIDB/04423/2020 and UIDP/04423/2020 under the project PTDC/SAU-PUB/28736/2017 (reference POCI-01-0145-FEDER-028736), cofinanced by COMPETE 2020, Portugal 2020 and the European Union through the ERDF and by FCT through national funds, as well as CHIRALBIOACTIVE-PI-3RL-IINFACTS-2019, and supported by the Applied Molecular Biosciences Unit-UCIBIO which is financed by national funds from FCT/MCTES (UID/Multi/04378/2019). Thanks are also due to FCT, the European Union, QREN, FEDER, COMPETE, by funding cE3c center (Ref. UID/BIA/00329/2019) and Direcao Regional da Ciencia e Tecnologia (Azores Government) by funding Azorean Biodiversity Group.info:eu-repo/semantics/publishedVersio

SF3B1-mutated chronic lymphocytic leukemia shows evidence of NOTCH1 pathway activation including CD20 downregulation

Chronic lymphocytic leukemia (CLL) is characterized by a low CD20 expression, in part explained by an epigenetic-driven downregulation triggered by mutations of the NOTCH1 gene. In the present study, by taking advantage of a wide and well-characterized CLL cohort (n=537), we demonstrate that CD20 expression is downregulated in SF3B1-mutated CLL in an extent similar to NOTCH1-mutated CLL. In fact, SF3B1-mutated CLL cells show common features with NOTCH1-mutated CLL cells, including a gene expression profile enriched of NOTCH1-related gene sets and elevated expression of the active intracytoplasmic NOTCH1. Activation of the NOTCH1 signaling and down-regulation of surface CD20 in SF3B1-mutated CLL cells correlate with over-expression of an alternatively spliced form of DVL2, a component of the Wnt pathway and negative regulator of the NOTCH1 pathway. These findings are confirmed by separately analyzing the CD20-dim and CD20-bright cell fractions from SF3B1-mutated cases as well as by DVL2 knock-out experiments in CLL-like cell models. Altogether, the clinical and biological features that characterize NOTCH1-mutated CLL may also be recapitulated in SF3B1-mutated CLL, contributing to explain the poor prognosis of this CLL subset and providing the rationale for expanding novel agents-based therapies to SF3B1-mutated CLL

Defining the scope of the European Antimicrobial Resistance Surveillance network in Veterinary medicine (EARS-Vet): a bottom-up and One Health approach

Background Building the European Antimicrobial Resistance Surveillance network in Veterinary medicine (EARS-Vet) was proposed to strengthen the European One Health antimicrobial resistance (AMR) surveillance approach. Objectives To define the combinations of animal species/production types/age categories/bacterial species/specimens/antimicrobials to be monitored in EARS-Vet. Methods The EARS-Vet scope was defined by consensus between 26 European experts. Decisions were guided by a survey of the combinations that are relevant and feasible to monitor in diseased animals in 13 European countries (bottom-up approach). Experts also considered the One Health approach and the need for EARS-Vet to complement existing European AMR monitoring systems coordinated by the ECDC and the European Food Safety Authority (EFSA). Results EARS-Vet plans to monitor AMR in six animal species [cattle, swine, chickens (broilers and laying hens), turkeys, cats and dogs], for 11 bacterial species (Escherichia coli, Klebsiella pneumoniae, Mannheimia haemolytica, Pasteurella multocida, Actinobacillus pleuropneumoniae, Staphylococcus aureus, Staphylococcus pseudintermedius, Staphylococcus hyicus, Streptococcus uberis, Streptococcus dysgalactiae and Streptococcus suis). Relevant antimicrobials for their treatment were selected (e.g. tetracyclines) and complemented with antimicrobials of more specific public health interest (e.g. carbapenems). Molecular data detecting the presence of ESBLs, AmpC cephalosporinases and methicillin resistance shall be collected too. Conclusions A preliminary EARS-Vet scope was defined, with the potential to fill important AMR monitoring gaps in the animal sector in Europe. It should be reviewed and expanded as the epidemiology of AMR changes, more countries participate and national monitoring capacities improve.Peer reviewe