Hydrazides and hydrazones as versatile Michael-Donors for iminium-catalyzed conjugate addition reactions

396 : il., graf.In the work compiled in this thesis is presented a series of strategies that have been studied and have lead to the asymmetric synthesis of useful building blocks in high yields and stereochemical control. These are reliant on the use of chiral secondary amines as the element that induces stereocontrol, where the activation of the substrate is based on the formation of an iminium ion intermediate within the catalytic cycle. In this sense, it has been demonstrated that, under this type of activation, hydrazides and hydrazones are efficient and versatile reagents that can be used as Michael donors in conjugate addition reactions.Thus, the performance of these hydrazide and hydrazone reagents as N-donors has been initially tested. In this context, two different aza-Michael initiated cascade reactions have been studied, using either N,N¿-disubstituted hydrazides or hydrazones derived from pyruvaldehyde in the reaction with -unsaturated aldehydes. Furthermore, the synthetic versatility of the products obtained has allowed a series of transformations to be performed, which is highlighted in the synthesis of valuable adducts (e.g. pyrazolines, pyrazolidinones or 1,3-diamines).On the other hand, the ability of hydrazones to act C-pro-nucleophiles for the same type of reaction has also been demonstrated. In this sense, the conjugate addition reaction between N-monosubstituted hydrazones and various enals via iminium activation has been studied, confirming that hydrazones containing an electron-withdrawing group at the azomethine position undergo this process in a highly efficient manner. Moreover, the importance of this methodology has been highlighted by the synthesis of a series of 1,4-dicarbonyl compounds, verifying that hydrazones can behave as acyl anion equivalents

Proyecto de intervención “Penélope”: Abordaje biopsicosocial de aspectos relacionados con la prostitución en mujeres usuarias del programa “Ulises” del Centro de Solidaridad de Zaragoza

Este trabajo trata de abordar varios aspectos relacionados con la prostitución en el colectivo de mujeres que se encuentran en tratamiento de mantenimiento con metadona, a través (programa Ulises) en el Centro de Solidaridad Proyecto Hombre de Zaragoza. En concreto, se ha diseñado un proyecto de intervención cuyo principal objetivo es la creación de un espacio grupal donde se puedan trabajar factores biopsicosociales para las mujeres usuarias del programa Ulises que han ejercido la prostitución, la están ejerciendo en la actualidad o tienen riesgo de ejercerla

Social Professionals in the Face of the Health Crisis

Due to the crisis generated by COVID-19 at a global level, many professionals are working under harsh conditions, and the Basque Country is no exception. On 14 March 2020, the head of the government decreed a state of alarm at the state level, which forced us all to be confined to our homes. This situation directly affected the profession of social educator. In fact, these professionals work with the most vulnerable groups, so working on the front line is mandated, even if this results in a significant risk. The situation of the groups in residential resources cannot be easy due to the stress produced by living together and being locked up, and this directly affects the educators who necessarily work in it. However, the over-exertion that all of this requires, which is a risk, has not been detected nor recognized at the social level. For this reason, the objective of this investigation is to measure the stress of social educators of advanced age who work in residential resources in different zones of the Basque Country (northern Spain). Sixty-seven social educators participated in the case study. Qualitative and quantitative methods were combined for data collection. This questionnaire was conducted through the Google Forms platform. The quantitative data collected through the questionnaire were analyzed by descriptive analysis and frequency contrasts were performed through the SPSS V25 program. We can conclude that it is necessary to take into account the difficulties of this sector and the professionals both at the governmental and social levels. Future research should include responses from both groups and workers in order to guarantee adequate inclusion

Scientific Evidence Supporting the Beneficial Effects of Isoflavones on Human Health

Isoflavones are phenolic compounds with a chemical structure similar to that of estradiol. They are present in several vegetables, mainly in legumes such as soy, white and red clover, alfalfa and beans. The most significant food source of isoflavones in humans is soy-derived products. Isoflavones could be used as an alternative therapy for pathologies dependent on hormonal disorders such as breast and prostate cancer, cardiovascular diseases, as well as to minimize menopausal symptoms. According to the results gathered in the present review, it can be stated that there is scientific evidence showing the beneficial effect of isoflavones on bone health and thus in the prevention and treatment of osteoporosis on postmenopausal women, although the results do not seem entirely conclusive as there are discrepancies among the studies, probably related to their experimental designs. For this reason, the results should be interpreted with caution, and more randomized clinical trials are required. By contrast, it seems that soy isoflavones do not lead to a meaningful protective effect on cardiovascular risk. Regarding cancer, scientific evidence suggests that isoflavones could be useful in reducing the risk of suffering some types of cancer, such as breast and endometrial cancer, but further studies are needed to confirm these results. Finally, isoflavones could be useful in reducing hot flushes associated with menopause. However, a limitation in this field is that there is still a great heterogeneity among studies. Lastly, with regard to isoflavone consumption safety, it seems that they are safe and that the most common adverse effect is mild and occurs at the gastrointestinal level.This study was supported by Instituto de Salud Carlos III (CIBERobn) under Grant CB12/03/30007, Basque Government under Grant PA20/04 and the University of the Basque Country under Grant GIU18-17

Caracterización de la morfología foveal: parametrización, diferencias de sexo y efectos de la edad

Frente a los análisis convencionales de grosores de la retina, el análisis morfológico de la fóvea presenta una metodología alternativa de gran potencial pero poco explorada. En este estudio se implementa un pipeline completo de análisis morfológico basado en imágenes OCT (Optical Coherence Tomography), comparando los modelos matemáticos existentes para estudiar la fóvea y demostrando su capacidad de ajuste y mejora de la fiabilidad test-retest. Asimismo, se analiza la influencia de la edad y el sexo en parámetros morfológicos como la altura, anchura, pendiente o área de la fóvea en una cohorte de 272 sujetos sanos. Los resultados muestran un claro dimorfismo sexual en la fóvea junto con relevantes cambios experimentados durante el envejecimiento

Ikaskuntza Zerbitzuan oinarritutako Gradu Amaierako Lanen azterketa, ikasleen identitate hezitzailea eraikitzeko eskaintzen dituzten aukerak

Higher Education is responsible in achieving the milestones specified in the 2030 Agenda for Sustainable Development, approved by the General Assembly of the United Nations. During Teacher Education, it seems that Service-Learning is an appropriate teaching method to make these objectives come true.In this work, we analyse the services that have been carried out in Ramon Bajo School, with the objective of knowing the experiences, and their effects on the professional identity development of the students who have developed their Final Degree Projects through Service- Learning. The 3 participants’ narratives have been organized into 4 categories that emerge from content analysis carried out: one self’s assessment, tutoring’s assessment, School experience’s assessment, and Service-Learning’s assessment. The results suggest that Final Degree Projects based on Service-Learning favour the perception about the development of certain skills, the awareness of cooperation’s importance, and the self-esteem strengthening both for the functionality of what has been learned, and for the opportunity to face personal challenges. Finally, some improvements are specified, identifying the elements that have hindered the students’ process.; Nazio Batuen Garapen Iraunkorrerako 2030 Agendan zehaztutako mugarrien lorpenerako, Unibertsitate Hezkuntzak erantzukizuna du. Hezitzaileen Formakuntzan, Ikaskuntza Zerbitzua irakaskuntza metodo egokitzat hartu izan da helburu horiek errealitate bilaka daitezen. Lan honetan, aztergai izan diren zerbitzuak Ramon Bajo eskolan aurrera eraman dira, helburua ondorengoa izanik: ezagutzea Ikaskuntza Zerbitzuan oinarritutako Gradu Amaierako Lanak burutu dituzten ikasleek izandako bizipenak eta horiek euren identitate hezitzailearen eraikuntzan izan duten efektua. Parte hartu duten 3 ikasleen istorioak gauzatutako eduki analisitik azaleratu diren 4 kategorien arabera antolatu dira: norberaren buruaren inguruko balorazioa, tutoretza prozesuaren balorazioa, ikastetxean izandako bizipenen balorazioa, eta Ikaskuntza Zerbitzuaren inguruko balorazioa. Agertutako emaitzetatik ondorioztatu daiteke Ikaskuntza Zerbitzuan oinarritutako Gradu Amaierako Lanei esker ikasleek hainbat konpetentzien garapena aitortzen dutela, lankidetzaren garrantziaz jabetu direla, eta autoestimua indartu egin dela bai ikasitakoaren funtzionalitateagatik, bai erronka pertsonalak gainditzeko aukera izan dutelako. Azkenik, hobetzekoak identifikatzen dira, ikasleen prozesuan oztopo izan diren elementuak oinarritzat hartuz

Exploiting Carbonyl Groups to Control Intermolecular Rhodium-Catalyzed Alkene and Alkyne Hydroacylation

Readily available β-carbonyl-substituted aldehydes are shown to be exceptional substrates for Rh-catalyzed intermolecular alkene and alkyne hydroacylation reactions. By using cationic rhodium catalysts incorporating bisphosphine ligands, efficient and selective reactions are achieved for β-amido, β-ester, and β-keto aldehyde substrates, providing a range of synthetically useful 1,3-dicarbonyl products in excellent yields. A correspondingly broad selection of alkenes and alkynes can be employed. For alkyne substrates, the use of a catalyst incorporating the Ampaphos ligand triggers a regioselectivity switch, allowing both linear and branched isomers to be prepared with high selectivity in an efficient manner. Structural data, confirming aldehyde chelation, and a proposed mechanism are provided

Anti-Obesity Effects of Macroalgae

Macroalgae have attracted great interest for their potential applications in nutraceutical and pharmaceutical industries as source of bioactive medicinal products and food ingredients. This review gathers data from in vitro and in vivo studies addressing the anti-obesity effects of macroalgae. Great consensus exists in all reported in vitro studies concerning the reduction induced by seaweed extracts in the expression of transcriptional factors controlling adipogenesis. In animals, macroalgae reduced body fat accumulation and prevented other obesity features, such as dyslipidemia, insulin resistance and fatty liver. These effects are not due to food intake reduction, since few studies have reported such event. Indeed, the effects on metabolic pathways in target tissues/organs seem to play a more relevant role. Macroalgae can reduce de novo lipogenesis, limiting fatty acid availability for triglyceride synthesis in white adipose tissue. This effect has been observed in both cell cultures and adipose tissue from animals treated with macroalgae extracts. In addition, increased fatty acid oxidation and thermogenic capacity, as well as a shift towards healthier gut microbiota composition may contribute to the body fat-lowering effect of macroalgae. Studies in humans are needed to determine whether macroalgae can represent a feasible tool to prevent and/or manage overweight and obesity.This study has been supported by grants from the Government of the Basque Country (ELKARTEK) under grant KK-2019/00031, Instituto de Salud Carlos III (CIBERobn) under Grant CB12/03/30007 and University of the Basque Country under Grant GIU18-173. M.G.-A. is a fellow from the University of the Basque Country

Comparative Effects of Pterostilbene and Its Parent Compound Resveratrol on Oxidative Stress and Inflammation in Steatohepatitis Induced by High-Fat High-Fructose Feeding

Different studies have revealed that oxidative stress and inflammation are crucial in NAFLD (Non-alcoholic fatty liver disease). The aim of this study is to analyze whether pterostilbene and resveratrol are able to either avoid or delay the progression of non-alcoholic liver steatosis towards steatohepatitis. This has been performed by examining their effects on oxidative stress, inflammation, fibrosis and pre-carcinogenic stages. Rats were distributed into five experimental groups and were fed with either a standard diet or a high-fat high-fructose diet, supplemented or not with pterostilbene (15 or 30 mg/kg/d) or resveratrol (30 mg/kg/d), for 8 weeks. Liver histological analysis was carried out by haematoxylin–eosin staining. Serum and hepatic oxidative stress-related parameters were assessed using spectrophotometry, and the expression of genes related to inflammation, fibrosis and cancer by qRT-PCR. The dietary model used in this study led to the development of steatohepatitis, where rats displayed oxidative stress, inflammation and ballooning, although not fibrosis. It also modified the expression of hepatocarcinoma-related genes. The results show, for the first time, that pterostilbene was able to partially prevent these alterations, with the exception of changes in hepatocarcinoma-related genes, mainly at 30 mg/kg/d. Pterostilbene was more effective than its parent compound resveratrol, probably due to its high bioavailability and higher anti-oxidant and anti-inflammatory activities, attributable to its different chemical structure.This study was supported by grants from the Ministerio de Economía y Competitividad (AGL-2015-65719-R), Fondo Europeo de Desarrollo Regional (FEDER), the Instituto de Salud Carlos III (CIBERobn) under Grant CB12/03/30007 and the University of the Basque Country under Grant GIU18-173

Spatial characterization of the effect of age and sex on macular layer thicknesses and foveal pit morphology

Characterizing the effect of age and sex on macular retinal layer thicknesses and foveal pit morphology is crucial to differentiating between natural and disease-related changes. We applied advanced image analysis techniques to optical coherence tomography (OCT) to: 1) enhance the spatial description of age and sex effects, and 2) create a detailed open database of normative retinal layer thickness maps and foveal pit shapes. The maculae of 444 healthy subjects (age range 21–88) were imaged with OCT. Using computational spatial data analysis, thickness maps were obtained for retinal layers and averaged into 400 (20 x 20) sectors. Additionally, the geometry of the foveal pit was radially analyzed by computing the central foveal thickness, rim height, rim radius, and mean slope. The effect of age and sex on these parameters was analyzed with multiple regression mixed-effects models. We observed that the overall age-related decrease of the total retinal thickness (TRT) (-1.1% per 10 years) was mainly driven by the ganglion cell-inner plexiform layer (GCIPL) (-2.4% per 10 years). Both TRT and GCIPL thinning patterns were homogeneous across the macula when using percentual measurements. Although the male retina was 4.1 μm thicker on average, the greatest differences were mainly present for the inner retinal layers in the inner macular ring (up to 4% higher TRT than in the central macula). There was an age-related decrease in the rim height (1.0% per 10 years) and males had a higher rim height, shorter rim radius, and steeper mean slope. Importantly, the radial analysis revealed that these changes are present and relatively uniform across angular directions. These findings demonstrate the capacity of advanced analysis of OCT images to enhance the description of the macula. This, together with the created dataset, could aid the development of more accurate diagnosis models for macular pathologies.This study was partially co-funded by the Instituto de Salud Carlos III (https://www.isciii.es) through the projects PI14/00679 (IG) and PI16/00005 (IG), by the Basque Foundation for Health Innovation and Research (https://www.bioef.org) through the project BIO17/ND/010 (IG), and by the Department of Health of the Basque Government (https://www.euskadi.eus/gobierno-vasco/departamento-salud) through the projects 2019111100 (IG), 2020333033(IG). The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript