New Insights into Trifluoromethyl Gold Chemistry

Se ha realizado un estudio exhaustivo de la química de trifluorometil complejos de oroque contienen entre uno y tres grupos CF3. Con ese objetivo, se han preparado loscomplejos de oro(I) [PPh4][CF3AuX] (X = Cl, Br, I), que son oxidados fácilmente porhalógenos, X2, para dar lugar a los complejos [PPh4][CF3AuX3] correspondientes.Mediante espectrometría de masas en tándem, los primeros conducen a los anionesmixtos [F−Au−X]− a través de la extrusión de CF2 en fase gas, mientras que los aniones[AuIIX3]− (X = Cl, Br) se generan por homólisis del enlace Au−C en los complejos deAu(III). Por reacción de [PPh4][CF3AuCF3] con XeF2 se ha preparado y caracterizadototalmente el primer difluoruro organometálico de oro(III) con disposición trans,[PPh4][trans-(CF3)2AuF2]. El estudio de la descomposición unimolecular del anión[trans-(CF3)2AuF2]− ha permitido detectar las especies [CF3AuFx]– (x = 1, 2, 3) en fasegas, así como los aniones [AuIIF3]− y [AuIF2]− en etapas posteriores del experimento.Además, los ligandos fluoruro en el complejo [PPh4][trans-(CF3)2AuF2] son sustituidosfácilmente por los halogenuros más pesados y por cianuro, con retención de laestereoquímica. De hecho, por comparación de las estructuras cristalinas de las especiesisolépticas e isomorfas [PPh4][trans-(CF3)2M(CN)2] (M = Ag, Au), se pudo concluirque Au(III) y Ag(III) tienen radios covalentes similares en su geometría plano cuadrada.La obtención del complejo [PPh4][(CF3)3AuI] por fotoadición oxidante de CF3I sobre[PPh4][CF3AuCF3] constituye la ruta de acceso más apropiada al fragmento (CF3)3Au.Esta especie de Au(III) abre la puerta a la síntesis de diferentes derivados aniónicos,cuyos análogos [(CH3)3AuX]− no se conocen. Además, se ha preparado el análogofluorado del trimetil oro, (CF3)3Au·OEt2, que es un sintón adecuado de la especieinsaturada de 14 electrones (CF3)3Au. Este fragmento es el ácido de Lewis R3Au (R =grupo organilo) más fuerte descrito hasta la fecha. Esta unidad (CF3)3Au, que presentaforma de T, se caracteriza por una marcada estabilidad estereoquímica y una bajatendencia a la eliminación reductora de CF3–CF3, contrariamente al comportamientoobservado para el análogo no fluorado (CH3)3Au. También se han preparado ycaracterizado diversos complejos neutros con ligandos de diferente capacidad dadora ydistintos átomos dadores, que presentan una estabilidad muy superior a sus análogos nofluorados. Los complejos aniónicos de Au(III) descritos presentan vías dedescomposición distintas en fase gas, donde solo ocurren procesos unimoleculares, y enfase condensada, donde son posibles caminos intermoleculares de menor energía.<br /

From floodplain to aquatic sediments: Radiogeochronological fingerprints in a sediment core from the mining impacted Sancho Reservoir (SW Spain)

The Sancho Reservoir (SW Spain) was built in 1962, about the time of maximum 137Cs fallout, and it has been affected by acid mine drainage (AMD) particularly since the mining cease in 2001. This is a unique scenario for studying the radiogeochronological fingerprints in AMD-affected sediments deposited over the former flood plain. A sediment core sampled in 2011 was analysed for bulk density, 137Cs, 239Pu, 240Pu, 210Pb, 226Ra, 228Ra, 234Th (238U) and 40K, and studied with various radiometric dating models. Bulk density revealed unsteady compaction and likely depositional events. The activity concentrations of 226Ra, 228Ra, 234Th (238U) and 40K were uniform down-core, but declining overall in the upper 0–25 cm, revealing changes in provenance except for 238U, which increased in the top 10 cm likely due to its supply by AMD. The AMD fingerprint was also found in the 239+240Pu/137Cs activity ratio, which increased in the top sediment layers. The 137Cs and 239+240Pu profiles show well defined peaks at the same depth, with inventories being about four times higher than the expected integrated atmospheric deposition in the area. The unsupported 210Pb (210Pbexc) showed a complex non-monotonic profile interrupted at several sections, particularly around the 137Cs peak. The whole dataset cannot be interpreted in terms of continuous sedimentation processes. Based upon correlated features in the bulk density and 210Pbexc profiles, a series of depositional events (likely linked to peaks in the rainfall records) have been identified in the core. These events date back to the period comprised since the construction of the dam until its increase in height in 1972, which likely displaced upstream the main depositional area of riverine loads, as inferred from sediment trap data. The CRS (with a reference date) and (a piecewise) CIC models have been used for complementing and discussing the chronology.Ministerio de Economia y Competitividad CTM2015-68628-

A Review of the Commercial Uses of Sulphate Minerals from the Titanium Dioxide Pigment Industry: The Case of Huelva (Spain)

This study was focused on the historical evolution of the waste management policy carried out by the Spanish industry devoted to titanium dioxide pigments manufacturing for minimising its environmental impact. This challenge was achieved by modifying the original chemical process and converting the originally dissolved sulphate and sulphuric acid present in the final streams of the factory into sulphate minerals (melanterite FeSO4 7H2O, szomolnokite FeSO4 H2O, and gypsum CaSO4 2H2O). These by-products were physicochemically, mineralogically and radiologically characterised in order to gain basic information for its subsequent commercial use. Some of the uses summarised in this study for both ferrous sulphates are as a supplier of iron to prevent chlorosis, animal food, manufacture of cement (to reduce Cr VI), primary flocculants for ferrous sulphates, magnetite nanoparticle and nano-Fe2O3 formation, production of magnetite concentrate, remediation of polluted soils with metals, and treatment of wastewaters. Red gypsum was analysed as a substitute for natural gypsum in the manufacture of cement, construction materials, inhibitor in soil erosion, and the immobilisation of heavy metals in agricultural soils and carbonation processes.This research was partially supported by the Spanish Government Department of Science and Technology (MINECO) through the project "Fluxes of Radionuclides Emitted by the Phosphogypsum Piles Located at Huelva; Assessment of the Dispersion, Radiological Risks and Remediation Proposals" (Ref. CTM, 2015-68628-R)), the Regional Government of Andalusia project called "Basic processes regulating the fractionations and enrichments of natural radionuclides under acid mine drainage conditions" (Ref.: UHU-1255876), and the University of Cadiz project called "New methodogy of radioisotope isolation with environmental interest for its measurement by alpha spectrometry" (Ref: PR2019-024). Documen

Demographic and clinical characteristics of patients with α1-antitrypsin deficiency genotypes PI*ZZ and PI*SZ in the Spanish registry of EARCO

Background: The Spanish registry of α1-antitrypsin deficiency (AATD) integrated in the European Alpha-1 Research Collaboration (EARCO) provides information about the characteristics of patients, in particular those with the PI*SZ genotype, which is frequent in Spain. Method: Individuals with severe AATD defined as proteinase inhibitor (PI) genotypes PI*ZZ, PI*SZ and other rare deficient variants were included from February 1, 2020, to February 1, 2022. The analysis focused on a comparison of the characteristics of PI*ZZ and PI*SZ patients. Results: 409 patients were included (53.8% men) with a mean±sd age of 53.5±15.9 years. Genotypes were PI*ZZ in 181 (44.7%), PI*SZ in 163 (40.2%), PI*SS in 29 (7.2%) and other in 32 (7.9%). 271 (67.4%) had lung disease: 175 chronic obstructive pulmonary disease (43.5%), 163 emphysema (40.5%) and 83 bronchiectasis (20.6%). Patients with the PI*SZ genotype were younger, more frequently non-index cases and had a lower frequency of respiratory diseases except asthma compared with PI*ZZ patients. Among patients with respiratory diseases, PI*SZ individuals were significantly older both at onset of symptoms and at diagnosis; only asthma was more frequent in PI*SZ than in PI*ZZ individuals. Twelve PI*SZ patients (15.4%) received augmentation therapy compared with 94 PI*ZZ patients (66.2%; p<0.001). Conclusions: There is a high prevalence of PI*SZ in Spain. Patients with the PI*SZ genotype were older at symptom onset and diagnosis and had less severe lung disease compared with PI*ZZ patients. The prevalence of asthma was higher in PI*SZ, and up to 15% of PI*SZ patients received augmentation therapy.Acknowledgements: The Spanish registry would like to acknowledge the support of the EARCO Steering committee: Christian Clarenbach and Marc Miravitlles (co-chairs), Robert Bals, Jan Stolk, Joanna Chorostowska-Wynimko, Karen O’Hara, Marion Wilkens, José Luis López-Campos, Alice M. Turner, Ilaria Ferrarotti, Gerry McElvaney and Robert A. Stockley

Bullying, cyberbullying y dating violence: Estudio de la gestión de la vida social en estudiantes de Primaria y Secundaria de Andalucía

Centro de Estudios Andaluces PRY040/1

Age and Chronodisruption in Mouse Heart: Effect of the NLRP3 Inflammasome and Melatonin Therapy

Age and age-dependent inflammation are two main risk factors for cardiovascular diseases. Aging can also affect clock gene-related impairments such as chronodisruption and has been linked to a decline in melatonin synthesis and aggravation of the NF- B/NLRP3 innate immune response known as inflammaging. The molecular drivers of these mechanisms remain unknown. This study investigated the impact of aging and NLRP3 expression on the cardiac circadian system, and the actions of melatonin as a potential therapy to restore daily rhythms by mitigating inflammaging. We analyzed the circadian expression and rhythmicity of clock genes in heart tissue of wild-type and NLRP3-knockout mice at 3, 12, and 24 months of age, with and without melatonin treatment. Our results support that aging, NLRP3 inflammasome, and melatonin affected the cardiac clock genes expression, except for Rev-erba, which was not influenced by genotype. Aging caused small phase changes in Clock, loss of rhythmicity in Per2 and Rora, and mesor dampening of Clock, Bmal1, and Per2. NLRP3 inflammasome influenced the acrophase of Clock, Per2, and Rora. Melatonin restored the acrophase and the rhythm of clock genes affected by age or NLRP3 activation. The administration of melatonin re-established murine cardiac homeostasis by reversing age-associated chronodisruption. Altogether, these results highlight new findings about the effects aging and NLRP3 inflammasome have on clock genes in cardiac tissue, pointing to continuous melatonin as a promising therapy to placate inflammaging and restore circadian rhythm in heart muscle. Additionally, light microscopy analysis showed age-related morphological impairments in cardiomyocytes, which were less severe in mice lacking NLRP3. Melatonin supplementation preserved the structure of cardiac muscle fibers in all experimental groups.Instituto de Salud Carlos III (Ministerio de Economia y Competitividad, Spain) (European Regional Development Fund/European Social Fund "Investing in your future") PI13-981 PI16-00519 PI19-01372 CB16-10-00238 CB16/10/00239Junta de Andalucia CTS-101Spanish Governmen

New Adenovirus Groups in Western Palaearctic Bats

In the context of long-term screening for viruses on Western Palaearctic bats, we tested for the presence of adenovirus 1392 oropharyngeal swabs and 325 stool samples taken from 27 bat species. Adenoviruses were detected in 12 species of the Vespertilionidae and the Rhinolophidae families. Fifty positive respiratory and 26 positive stool samples were studied. Phylogenetic analyses of partial hexon protein and partial DNA-dependent DNA polymerase genes indicate that all these bat adenoviruses belong to the genus Mastadenovirus but without constituting a monophyletic cluster. According to genetic identities, the new groups are distinct to the previously described Bat mastadenovirus A and B species and contribute with potentially new members. Our data support that diversity of bat mastadenovirus is host-dependent and increase the knowledge of potentially pathogenic virus from bats. Due to the active role of bats as viral reservoirs, the characterization of these viruses is relevant for Public Health.This project was financially supported by an agreement between the Public Health Department of the Spanish Ministry of Health and the Instituto de Salud Carlos III for the development of "Rabies Surveillance in Spain" and by projects SAF 2006-12784-C02-01, SAF 2006-12784-C02-02, SAF 2009-09172 and SAF2013-47194-P of the General Research Programme of the Spanish Ministry of Science and Education

Subpixel real-time jitter detection algorithm and implementation for polarimetric and helioseismic imager

The polarimetric and helioseismic imager instrument for the Solar Orbiter mission from the European Space Agency requires a high stability while capturing images, specially for the polarimetric ones. For this reason, an image stabilization system has been included in the instrument. It uses global motion estimation techniques to estimate the jitter in real time with subpixel resolution. Due to instrument requirements, the algorithm has to be implemented in a Xilinx Virtex-4QV field programmable gate array. The algorithm includes a 2-D paraboloid interpolation algorithm based on 2-D bisection. We describe the algorithm implementation and the tests that have been made to verify its performance. The jitter estimation has a mean error of 125  pixel of the correlation tracking camera. The paraboloid interpolation algorithm provides also better results in terms of resources and time required for the calculation (at least a 20% improvement in both cases) than those based on direct calculation

Clinical and functional characteristics of individuals with alpha-1 antitrypsin deficiency: EARCO international registry

Background: Alpha-1 antitrypsin deficiency (AATD) is a rare disease that is associated with an increased risk of pulmonary emphysema. The European AATD Research Collaboration (EARCO) international registry was founded with the objective of characterising the individuals with AATD and investigating their natural history. Methods: The EARCO registry is an international, observational and prospective study of individuals with AATD, defined as AAT serum levels < 11 μM and/or proteinase inhibitor genotypes PI*ZZ, PI*SZ and compound heterozygotes or homozygotes of other rare deficient variants. We describe the characteristics of the individuals included from February 2020 to May 2022. Results: A total of 1044 individuals from 15 countries were analysed. The most frequent genotype was PI*ZZ (60.2%), followed by PI*SZ (29.2%). Among PI*ZZ patients, emphysema was the most frequent lung disease (57.2%) followed by COPD (57.2%) and bronchiectasis (22%). Up to 76.4% had concordant values of FEV1(%) and KCO(%). Those with impairment in FEV1(%) alone had more frequently bronchiectasis and asthma and those with impairment in KCO(%) alone had more frequent emphysema and liver disease. Multivariate analysis showed that advanced age, male sex, exacerbations, increased blood platelets and neutrophils, augmentation and lower AAT serum levels were associated with worse FEV1(%). Conclusions: EARCO has recruited > 1000 individuals with AATD from 15 countries in its first 2 years. Baseline cross sectional data provide relevant information about the clinical phenotypes of the disease, the patterns of functional impairment and factors associated with poor lung function.Funding: The International EARCO registry is funded by unrestricted grants of Grifols, CSL Behring, Kamada, pH Pharma and Takeda to the European Respiratory Society (ERS). Acknowledgements: The authors would like to thank the patients who participated in this study and the EARCO study investigators (listed below). We wish to acknowledge Elise Heuvelin from the ERS ofce (Lausanne, Switzterland) for her support in the management of EARCO, and Gemma Vilagut and Christina Founti (Bioclever, Barcelona, Spain) for their support in EARCO data monitoring. We also acknowledge the participation of Eduardo Loeb (Barcelona, Spain) in the development of the database and the monitoring of the data. List of EARCO study investigators: Georg-Christian Funk (Austria), Wim Jans sens, Silvia Pérez-Bogerd (Belgium), Leidy Prada (Colombia), Ana Hecomovic (Croatia), Eva Bartosovska, Jan Chlumsky, (Czech Republic), Alan Altraja, Jaanus Martti (Estonia), Angelo G. Corsico, Ilaria Ferrarotti, Simone Scarlata, Mario Malerba (Italy), Jan Stolk, Emily F van’t Wout (Netherlands), Joanna Chorowstoska-Wyminko (Poland), Catarina Guimaraes, Maria Sucena, Ana Caldas Raquel Marçoa, Isabel Ruivo dos Santos, Bebiana Conde, Maria Joana Reis Amado Maia Da Silva, Rita Boaventura (Portugal), Ruxandra Ulmeanu (Romania), María Torres-Duran, Marc Miravitlles, Miriam Barrecheguren, Juan Luis Rodriguez-Hermosa, Myriam Calle-Rubio, José María Hernández-Pérez, José Luis López-Campos, Francisco Casas-Maldonado, Ana Bustamante, Carlota Rodriguez-García, Cristina Martinez-González, Cruz González, Eva Tabernero, Lourdes Lázaro, Virginia Almadana, Mar Fernández-Nieto, Francisco Javier Michel de la Rosa, Carlos Martíez-Rivera, Layla Diab, María Isabel Parra (Spain), Hanan Tanash, Eeva Piitulainen (Sweden), Christian F. Clarenbach (Switzerland), Serap Argun Baris, Dilek Karadogan, Sebahat Genç (Turkey), Alice M. Turner, Beatriz Lara, David G. Parr (United Kingdom). EARCO Steering committee: Christian F Clarenbach and Marc Miravitlles (Co-chairs), Robert Bals, Jan Stolk, Joanna Chorostowska-Wynimko, Karen O’Hara, Marion Wilkens, José Luis López-Campos, Alice M. Turner, Ilaria Ferrarotti, Gerry McElvaney and Robert A. Stockle

Radiation tests on commercial instrumentation amplifiers, analog switches &amp; DAC's

A study of several commercial instrumentation amplifiers (INA110, INA111, INA114, INA116, INA118 & INA121) under neutron and vestigial gamma radiation was done. Some parameters (Gain, input offset voltage, input bias currents) were measured on-line and bandwidth, and slew rate were determined before and after radiation. The results of the testing of some voltage references REF102 and ADR290GR and the DG412 analog switch are shown. Finally, different digital-to-analog converters were tested under radiation