South-South Agreements in the Framework of North-South Integration: the Case of Morocco in the Euro-Mediterranean process

The hub and spokes structure that characterises Euro-Mediterranean relations is often attributed to the lack of integration among Arab countries. Successive regional projects implemented in areas like the Maghreb have been supported by empirical evidence on the potential welfare effects of trade and the costs of non-integration. However, the high interest in these aspects contrasts with a limited effort to investigate the root causes of non-integration. The aim of this work is to understand the reasons behind the apparent contradiction between the potential of South-South regionalism and the limited scope of its achievements in the Euro-Mediterranean area. The case of Morocco shows the role of preferential agreements in the continuity of economic relations prior to decolonisation and the contribution of South-South agreements to the reinforcement of the prevailing schemes of North-South integration in the area

A nobreza, o rei e a fronteira no medievo peninsular

The full fixation of the frontier between Portugal and Castile in the last third of the thirteenth century did not impede the great mobility of members of the Portuguese nobility, who established themselves in Castile temporarily or definitively due to the political conflicts in Portugal. The study of various cases relating to fourteenth-century nobles: Castro, Albuquerque, Teles de Menezes, Pacheco.La plena fijación de la frontera entre Portugal y Castilla en el último tercio del siglo XIII no impidió una gran movilidad de miembros de la nobleza portuguesa, que se establecen en Castilla temporal o definitivamente a consecuencia de conflictos políticos en Portugal. Estudio de varios casos relativos a nobles del siglo XIV: Castro, Albuquerque, Teles de Menezes, Pacheco

Design and Characterization of Lubricants Based on Functionalized Nanoparticles

The main objective of this PhD thesis is to design and characterize efficient nanolubricants based on three polyalphaolefins (PAOs) and nanoparticles (NPs) of metal oxides or ceramics coated with organic acids for wind turbine gearboxes and electric transmissions of electric vehicles. First, preliminary tests and an in-depth literature survey on the time stability and tribological behavior of nanodispersions containing chemically modified nanoadditives were performed. Then, the thermophysical and tribological properties of PAO nanolubricants containing coated NPs (ZnO-OA, TiO2-OA, or SiO2-SA) were evaluated; in addition, possible tribological mechanisms were analyzed by confocal Raman microscopy. All the coated NPs studied improve the tribological behavior of their base oil, being the best the SiO2-SA NPs

Hydrazones as Singular Reagents in Asymmetric Organocatalysis

This Minireview summarizes strategies and developments regarding the use of hydrazones as reagents in asymmetric organocatalysis, their distinct roles in nucleophile–electrophile, cycloaddition, and cyclization reactions. The key structural elements governing the reactivity of these reagents in a preferred pathway will be discussed, as well as their different interactions with organocatalysts, leading to diverse activation modes. Along these studies, the synthetic equivalence of N-monoalkyl, N,N-dialkyl, and N-acyl hydrazones with several synthons is also highlighted. Emphasis is also put on the mechanistic studies performed to understand the observed reactivities. Finally, the functional group transformations performed from the available products has also been analyzed, highlighting the synthetic value of these methodologies, which served to access numerous families of valuable multifunctional compounds and nitrogen-containing heterocycles.Ministerio de Economía y Competitividad CTQ2013-48164-C2-1-P, CTQ201348164-C2-2-PEuropean FEDER fundsJunta de Andalucía 2012/FQM 107

La importancia de áreas de bosque en paisajes urbanos para la estructuración de metacomunidades de anfibios

Trabajo de Conclusión de Curso presentado como requisito parcial para la obtención del título de Licenciatura en Ciencias Biológicas – Ecología y Biodiversidad en la Universidad Federal de Integración Latino-Americana (UNILA). Orientador Prof. Dr. Michel Varajão GareyLa variación en la composición de metacomunidades es influenciada por un conjunto de factores bióticos, abióticos y por la capacidad de dispersión entre las manchas de hábitat. Sin embargo, se conoce poco al respecto de la dinámica de metacomunidades en paisajes urbanos. Con el objetivo de determinar la influencia de los factores ambientales (características de los cuerpos de agua, del paisaje circundante incluyendo el grado de urbanización) y los factores espaciales (distancia y arreglo espacial de los cuerpos de agua) en la variación de composición de especies en metacomunidades de anfibios, el presente trabajo buscó testar dos predictores: (i) la variación en la composición en la metacomunidades de los anuros será mayormente explicada por los factores ambientales que los factores espaciales; (ii) las variables del paisaje serán más importantes que las características estructurales de los cuerpos de agua en la determinación de la composición de especies en la metacomunidad de anuros. Para ello, fueron muestreados 16 cuerpos de agua en Foz do Iguazú y fueron registradas 15 especies de anuros pertenecientes a cinco familias, siendo la riqueza media por cuerpo de agua 4,56 ± 3,07. Los resultados obtenidos demuestran que la variación en la composición en áreas urbanas es mejor explicada por las variables del paisaje (14%), seguido por las variables espaciales (10%), y por último por las variables estructurales del cuerpo de agua (8%). La cantidad de áreas de bosque en el paisaje circundante y la profundidad de los cuerpos de agua son determinantes en la variación en la composición de metacomunidades de anuros existentes en las zonas urbanas y periurbanas de Foz de Iguazú. Nuestros resultados resaltan la importancia de crear y conservar bosques urbanos y periurbanos para la dinámica de la metacomunidad de anuros en ambientes urbanosA variação na composição nas metacomunidades é influenciada por um conjunto de fatores bióticos, abióticos e com a capacidade de dispersão entre as manchas de habitat. Porém, pouco se sabe a respeito da dinâmica de metacomunidades em paisagens urbanizadas. A fim de determinar a influência de fatores ambientais (características dos corpos de água, a paisagem circundante, incluindo o grau de urbanização) e fatores espaciais (distância e arranjo espacial dos corpos de água) na variação da composição de espécies em metacomunidades de anfíbios, o presente trabalho buscou testar dois preditores: (i) a variação na composição nas metacomunidades de anuros será maiormente explicada por fatores ambientais do que por fatores espaciais; (ii) as variáveis da paisagem serão mais importantes que as características estruturais dos corpos de água na determinação da composição de espécies na metacomunidad de anuros. Para tanto, 16 corpos de água foram amostrados em Foz do Iguaçu e foram registradas 15 espécies de anuros pertencentes a cinco famílias, com a riqueza média por corpo de água 4,56 ± 3,07. Os resultados obtidos demostram que a variação na composição em areas urbanas é melhor explicada pelas variáveis da paisagem (14%), depois pelas variáveis espaciais (10%), e por último pelas variáveis estruturais do corpo de água (8%). La quantidade de área de mata e a profundidade dos corpos de água são determinantes na variação na composição das metacomunidades dos anuros existentes nas areas urbanas e periurbanas de Foz do Iguaçu. Nossos resultados resultados resaltam a importancia de se criar e conservar matas urbanas e periurbanas para a dinâmica da metacomunidade de anuros em ambientes urbano

Synthesis of IAN-type N,N-Ligands via Dynamic Kinetic Asymmetric Buchwald-Hartwig Amination

The Pd-catalyzed coupling of racemic heterobiaryl bromides, triflates, or nonaflates with aryl/alkyl primary amines using QUINAP as the ligand provides the corresponding axially chiral heterobiaryl amines with excellent yields and enantioselectivities. Reactivity and structural studies of neutral and cationic oxidative addition intermediates support a dynamic kinetic asymmetric amination mechanism based on the labilization of the stereogenic axis in the latter and suggest that coordination of the amine to the Pd center is the stereodetermining step.Ministerio de Ciencia e Innovación CTQ2013-48164-C2-1-P, CTQ2013-48164-C2-2-P, RYC-2013-12585 for A.R.European FEDER FundsJunta de Andalucía 2012/FQM 1078

PFASs: What can we learn from the European Human Biomonitoring Initiative HBM4EU

Per- and polyfluoroalkyl substances (PFASs) were one of the priority substance groups selected which have been investigated under the ambitious European Joint programme HBM4EU (2017–2022). In order to answer policy relevant questions concerning exposure and health effects of PFASs in Europe several activities were developed under HBM4EU namely i) synthesis of HBM data generated in Europe prior to HBM4EU by developing new platforms, ii) development of a Quality Assurance/Quality Control Program covering 12 biomarkers of PFASs, iii) aligned and harmonized human biomonitoring studies of PFASs. In addition, some cohort studies (on motherchild exposure, occupational exposure to hexavalent chromium) were initiated, and literature researches on risk assessment of mixtures of PFAS, health effects and effect biomarkers were performed. The HBM4EU Aligned Studies have generated internal exposure reference levels for 12 PFASs in 1957 European teenagers aged 12–18 years. The results showed that serum levels of 14.3% of the teenagers exceeded 6.9 μg/L PFASs, which corresponds to the EFSA guideline value for a tolerable weekly intake (TWI) of 4.4 ng/kg for some of the investigated PFASs (PFOA, PFOS, PFNA and PFHxS). In Northern and Western Europe, 24% of teenagers exceeded this level. The most relevant sources of exposure identified were drinking water and some foods (fish, eggs, offal and locally produced foods). HBM4EU occupational studies also revealed very high levels of PFASs exposure in workers (P95: 192 μg/L in chrome plating facilities), highlighting the importance of monitoring PFASs exposure in specific workplaces. In addition, environmental contaminated hotspots causing high exposure to the population were identified. In conclusion, the frequent and high PFASs exposure evidenced by HBM4EU strongly suggests the need to take all possible measures to prevent further contamination of the European population, in addition to adopting remediation measures in hotspot areas, to protect human health and the environment. HBM4EU findings also support the restriction of the whole group of PFASs. Further, research and definition for additional toxicological dose-effect relationship values for more PFASs compounds is neededEuropean Union’s Horizon 2020 research and innovation program under grant agreement No 73303

Cross-sectional associations between exposure to per- and polyfluoroalkyl substances and body mass index among European teenagers in the HBM4EU aligned studies

Per-and polyfluoroalkyl substances (PFAS) are widespread pollutants that may impact youth adiposity patterns. We investigated cross-sectional associations between PFAS and body mass index (BMI) in teenagers/adolescents across nine European countries within the Human Biomonitoring for Europe (HBM4EU) initiative. We used data from 1957 teenagers (12-18 yrs) that were part of the HBM4EU aligned studies, consisting of nine HBM studies (NEBII, Norway; Riksmaten Adolescents 2016-17, Sweden; PCB cohort (follow-up), Slovakia; SLO CRP, Slovenia; CROME, Greece; BEA, Spain; ESTEBAN, France; FLEHS IV, Belgium; GerES V-sub, Germany). Twelve PFAS were measured in blood, whilst weight and height were measured by field nurse/physician or self-reported in ques-tionnaires. We assessed associations between PFAS and age-and sex-adjusted BMI z-scores using linear and logistic regression adjusted for potential confounders. Random-effects meta-analysis and mixed effects models were used to pool studies. We assessed mixture effects using molar sums of exposure biomarkers with toxicological/structural similarities and quantile g-computation. In all studies, the highest concentrations of PFAS were PFOS (medians ranging from 1.34 to 2.79 mu g/L). There was a tendency for negative associations with BMI z-scores for all PFAS (except for PFHxS and PFHpS), which was borderline significant for the molar sum of [PFOA and PFNA] and significant for single PFOA [beta-coefficient (95% CI) per interquartile range fold change =-0.06 (-0.17, 0.00) and-0.08 (-0.15,-0.01), respectively]. Mixture assessment indicated similar negative associations of the total mixture of [PFOA, PFNA, PFHxS and PFOS] with BMI z-score, but not all compounds showed associations in the same direction: whilst [PFOA, PFNA and PFOS] were negatively associated, [PFHxS] associated positively with BMI z-score. Our results indicated a tendency for associations of relatively low PFAS concentrations with lower BMI in European teenagers. More prospective research is needed to investigate this potential relationship and its implications for health later in life.European Commission 733032Swedish Research Council European Commission 2017-0082

Dynamic Kinetic Resolution of Hetero biaryl Ketones by Zinc- Catalyzed Asymmetr ic Hydrosil ylation

Adiastereo- and highly enantioselective dynamic kinetic resolution (DKR) of configurationally labile hetero- biaryl ketones is described. The DKR proceeds by zinc- catalyze dhydrosilylation of the carbonyl group ,thus leading to secondary alcohols bearing axial and central chirality .The strategy relies on the labilization of the stereogenic axis that takes place thanks to aLewis acid–base interaction between anitrogen atom in the heterocycle and the ketone carbonyl group .The synthetic utility of the methodology is demonstrated through stereospecific transformations into either N,N-ligands or appealing axially chiral, bifunctional thiourea organocata- lysts.Ministerio de Ciencia e Innovación (Grants CTQ2016-76908-C2-1-P, CTQ2016-76908-C2-2-P, contract RYC-2013-12585)European FEDER FundsJunta de Andalucía (Grant 2012/FQM 10787)European Union - Marie Skłodowska-Curie (COFUND—Grant Agreement n 8 8 291780

Retos espaciales de la política de clústeres productivos: El caso del sector aeroespacial en la Comunidad de Madrid

Hoy en día, la política de promoción y desarrollo de clústeres productivos ha sido ampliamente aceptada por empresarios y gobiernos como una de las estrategias clave para mejorar la competitividad económica de un territorio. Es muy abundante la literatura especializada que trata el fenómeno de los clústeres desde el punto de vista de política industrial, sin embargo, son escasos los estudios sobre los efectos que la localización espacial de estos conglomerados tiene en los territorios urbanos. La presente comunicación tiene como objetivo explorar si existen condiciones de localización específicas, dentro de las metrópolis actuales, que se adecúen a las necesidades particulares de cada tipo de clústeres, consiguiendo así que se impulse su nivel competitividad económica sin interferir con los criterios básicos que persigue la sostenibilidad urbana. La tesis subyacente es que el modelo predominante de parques tecnológicos, ubicado en las periferias metropolitanas, no es el único posible ni el más deseable. A pesar de la amplia aceptación de este modelo en las regiones españolas, existen alternativas que permitan recuperar y poner en valor los antiguos tejidos productivos que han sido abandonados en las áreas urbanas consolidadas. Para contrastar esta tesis se ha analizado el clúster aeroespacial que opera en la Comunidad de Madri