Performance of point charge embedding schemes for excited states in molecular organic crystals

Modeling excited state processes in molecular crystals is relevant for several applications. A popular approach for studying excited state molecular crystals is to use cluster models embedded in point charges. In this paper, we compare the performance of several embedding models in predicting excited states and S1-S0 optical gaps for a set of crystals from the X23 molecular crystal database. The performance of atomic charges based on ground or excited states was examined for cluster models, Ewald embedding, and self-consistent approaches. We investigated the impact of various factors, such as the level of theory, basis sets, embedding models, and the level of localization of the excitation. We consider different levels of theory, including time-dependent density functional theory and Tamm-Dancoff approximation (TDA) (DFT functionals: ωB97X-D and PBE0), CC2, complete active space self-consistent field, and CASPT2. We also explore the impact of selection of the QM region, charge leakage, and level of theory for the description of different kinds of excited states. We implemented three schemes based on distance thresholds to overcome overpolarization and charge leakage in molecular crystals. Our findings are compared against experimental data, G0W0-BSE, periodic TDA, and optimally tuned screened range-separated functionals

Engineering the electronic and optical properties of 2D porphyrin paddlewheel metal-organic frameworks

Metal organic frameworks (MOFs) are promising photocatalytic materials due to their high surface area and tuneability of their electronic structure. We discuss here how to engineer the band structures and optical properties of a family of two-dimensional (2D) porphyrin-based MOFs, consisting of M tetrakis(4 carboxyphenyl) porphyrin structures (M TCPP, where M = Zn or Co) and metal (Co, Ni, Cu or Zn) paddlewheel clusters, with the aim of optimising their photocatalytic behaviour in solar fuel synthesis reactions (water splitting and/or CO2 reduction). Based on density functional theory (DFT) and time-dependent DFT simulations with a hybrid functional, we studied three types of composition/structural modifications: a) varying the metal centre at the paddlewheel or at the porphyrin centre to modify the band alignment; b) partially reducing the porphyrin unit to chlorin, which leads to stronger absorption of visible light; and c) substituting the benzene bridging between the porphyrin and paddlewheel, by ethyne or butadiyne bridges, with the aim of modifying the linker to metal charge transfer behaviour. Our work offers new insights on how to improve the photocatalytic behaviour of porphyrin- and paddlewheel-based MOFs

NeuroBoricuas: a novel approach for incorporating neuroscience education in schools of Puerto Rico

[EN] Puerto Rico is in dire need of transforming its education system to counter the current economic recession and ensure a future with talented Puerto Ricans at the forefront of scientific research and technology development.  Here we present a group of neuroscientists and educators, the NeuroBoricuas, committed to revolutionize the scientific culture of Puerto Rico by incorporating neuroscience research training and inquiry-based activities in public and private schools. We carry out our vision through diverse methods, such as community outreach activities, where we promote neuroscience literacy using diverse learning activities. In parallel, we are designing a neuroscience course and textbook with educators to be implemented in schools. We also established neuroscience laboratories in K-12 schools and trained science teachers to manage such laboratories, using equipment from the company “Backyard Brains”. These laboratory experiences are integrated into the academic curriculum in high schools and the equipment is also available for students interested in designing their independent research projects. Lastly, we are expanding a network of committed scientists who partner with educators to help nurture future neuroscientists early in their academic endeavors. Here, we describe our trajectory and our approach to transform scientific education in Puerto Rico.We thank Dr. Gregory J. Quirk, Dr. Daniel Colon-Ramos and Dr. Mark Miller for their support. We thank Tim Marzullo, from Backyard Brains, for supporting NeuroBoricuas. We also thank Palabreria, Digi-Serv and Puerto Rico 4.0 for their constant support. We thank all the NeuroBoricuas that selflessly work hard for a better Puerto Rico. This work has been supported by generous donations from the Puerto Rican people, a grant from the University of Puerto Rico Medical Sciences Campus’ Chancellor’s office, and the Grass Foundation.http://ocs.editorial.upv.es/index.php/HEAD/HEAD18Bravo-Rivera, C.; Díaz-Ríos, M.; Aldarondo-Hernández, A.; Santos-Vera, B.; Ramos-Medina, L.; De Jesús-Burgos, M.; Bravo-Rivera, H.... (2018). NeuroBoricuas: a novel approach for incorporating neuroscience education in schools of Puerto Rico. Editorial Universitat Politècnica de València. 1447-1455. https://doi.org/10.4995/HEAD18.2018.8223OCS1447145

Biochemical and structural characterization of a novel thermophilic esterase EstD11 provide catalytic insights for the HSL family

19 pags., 12 figs., 2 tabs.A novel esterase, EstD11, has been discovered in a hot spring metagenomic library. It is a thermophilic and thermostable esterase with an optimum temperature of 60°C. A detailed substrate preference analysis of EstD11 was done using a library of chromogenic ester substrate that revealed the broad substrate specificity of EstD11 with significant measurable activity against 16 substrates with varied chain length, steric hindrance, aromaticity and flexibility of the linker between the carboxyl and the alcohol moiety of the ester. The tridimensional structures of EstD11 and the inactive mutant have been determined at atomic resolutions. Structural and bioinformatic analysis, confirm that EstD11 belongs to the family IV, the hormone-sensitive lipase (HSL) family, from the α/β-hydrolase superfamily. The canonical α/β-hydrolase domain is completed by a cap domain, composed by two subdomains that can unmask of the active site to allow the substrate to enter. Eight crystallographic complexes were solved with different substrates and reaction products that allowed identification of the hot-spots in the active site underlying the specificity of the protein. Crystallization and/or incubation of EstD11 at high temperature provided unique information on cap dynamics and a first glimpse of enzymatic activity in vivo. Very interestingly, we have discovered a unique Met zipper lining the active site and the cap domains that could be essential in pivotal aspects as thermo-stability and substrate promiscuity in EstD11.We thank the staff from ALBA synchrotron facility (Barcelona, Spain) for support during crystallographic data collection. This work was funded by the UE through the HotDrops Project (FP7- PEOPLE-2012-IAPP, project number 324439). Additionally, this work was supported by the BFU2017-90030-P grant to J.A.H. from the Spanish Ministry of Science and Innovatio

Biochemical and structural characterization of a novel thermophilic esterase EstD11 provide catalytic insights for the HSL family

[Abstract]: A novel esterase, EstD11, has been discovered in a hot spring metagenomic library. It is a thermophilic and thermostable esterase with an optimum temperature of 60 C. A detailed substrate preference analysis of EstD11 was done using a library of chromogenic ester substrate that revealed the broad substrate specificity of EstD11 with significant measurable activity against 16 substrates with varied chain length, steric hindrance, aromaticity and flexibility of the linker between the carboxyl and the alcohol moiety of the ester. The tridimensional structures of EstD11 and the inactive mutant have been determined at atomic resolutions. Structural and bioinformatic analysis, confirm that EstD11 belongs to the family IV, the hormone-sensitive lipase (HSL) family, from the α/β-hydrolase superfamily. The canonical a/b hydrolase domain is completed by a cap domain, composed by two subdomains that can unmask of the active site to allow the substrate to enter. Eight crystallographic complexes were solved with different substrates and reaction products that allowed identification of the hot-spots in the active site underlying the specificity of the protein. Crystallization and/or incubation of EstD11 at high temperature provided unique information on cap dynamics and a first glimpse of enzymatic activity in vivo. Very interestingly, we have discovered a unique Met zipper lining the active site and the cap domains that could be essential in pivotal aspects as thermo-stability and substrate promiscuity in EstD11Ministerio de Ciencia e Innovación; BFU2017-90030-

Aplicación de las tecnologías de la información geográfica en el diseño de itinerarios para la educación en paisaje en el ámbito de los Parques Nacionales

El proyecto pretende acercar los distintos tipos de paisajes a los estudiantes a partir de un itinerario y realizar una explicación a través de diversas actividades, que estarán disponibles online, de forma que se puedan trabajar los parques tanto de forma virtual como real. Los medios con los que contamos se basan en el trabajo realizado en el PIMCD anterior (PIMCD 224/2015 La potencialidad de la nube para el trabajo de campo en Geografía: El Parque Nacional de la Sierra de Guadarrama), centrado sobre el PN Sierra de Guadarrama, cuya metodología y recursos pedagógicos empleados serán enriquecidos y reutilizados en este proyecto en el que se continuará empleando las tecnologías de la información geográfica para el diseño de itinerarios geográficos que pongan al alcance de los docentes los paisajes de los Parques Nacionales, en el primer centenario de la Ley que crea su figura (primera Ley de Parques Nacionales se promulga en 1916). Tomando como punto de partida el concepto de paisaje que acuerda el Convenio Europeo del Paisaje (CEP) y las premisas didácticas que el mismo expone relativas a la inscripción de los aprendizajes necesarios, somos conscientes de la multiplicidad de recursos de que hoy disponemos para contribuir positivamente a desarrollar la sensibilidad y el sentido ético de los estudiantes y el profesorado hacia los paisajes en general y los espacios naturales protegidos en particular. Multiplicidad que responde tanto a la creciente disponibilidad de recursos web e información geográfica que ofrece la nube, como a la accesibilidad a nuevos dispositivos como GPS, tabletas o smartphones, que han supuesto una generalización en el acceso a información georreferenciada. Partiendo de esta realidad, nuestro proyecto se vertebra en dos líneas preferentes. Por un lado, acercar esta diversidad de nuevas tecnologías y la información geográfica o geoinformación al profesorado y alumnado, ofreciendo recursos que sirvan para el aprendizaje de su manejo dentro y fuera del aula y, por otro, mejorar el conocimiento de los valores naturales y culturales de distintos espacios singulares y sus paisajes, fomentando una conciencia social conservacionista tal y como contempla entre sus objetivos principales la Red de Parques Nacionales de España

Diseño de un modelo didáctico para la educación en paisaje utilizando Sigweb

A través del PIMCD 113, se ha diseñado e implementado un modelo didáctico para la educación en paisaje enfocado a alumnos del Grado de Maestro de Educación Primaria

Aliskiren affects fatty-acid uptake and lipid-related genes in rodent and human cardiomyocytes

International audienceWe investigated whether the direct renin inhibitor aliskiren can affect metabolism in cardiomyocytes from rat, mouse and human sources. METHODS AND RESULTS: At 10-50μmol/L, aliskiren significantly increased medium-chain-fatty-acid uptake in primary-cultured neonatal-rat and HL-1 adult-mouse-derived cardiomyocytes (BODIPY-induced fluorescence intensity). The fatty-acid transporter CD-36 was correspondingly translocated to, but the glucose transporter Glut-4 away from, the sarcoplasmic reticulum/plasma membrane, in primary-cultured neonatal-rat (CD-36, Glut-4) and adult-human (CD-36) cardiomyocytes (confocal immunocytochemistry). Immunoblotting showed that aliskiren induced phosphorylation of ERK1/2 in cardiomyocytes from all three sources; responses were dose- and time-dependent, unaffected by renin treatment, and did not cause alterations in expression of (P)R or Igf2/M6P receptors. Microarray analysis of the complete genome of aliskiren-treated neonatal-rat cardiomyocytes, with RT-qPCR and immunoblot confirmation assays in rat and human primary cardiomyocytes, showed that aliskiren up-regulated mRNA and increased protein expression of several enzymes important in lipid and glucose metabolism and in cholesterol biosynthesis. Cardiomyocyte cell-cycle and viability were unaffected by aliskiren

Self-Reported Health Status in Primary Health Care: The Influence of Immigration and Other Associated Factors

OBJECTIVE: The aims of this study are to compare self-reported health status between Spanish-born and Latin American-born Spanish residents, adjusted by length of residence in the host country; and additionally, to analyse sociodemographic and psychosocial variables associated with a better health status. DESIGN: This is a cross-sectional population based study of Latin American-born (n = 691) and Spanish-born (n = 903) in 15 urban primary health care centres in Madrid (Spain), carried out between 2007 and 2009. The participants provided information, through an interview, about self-reported health status, socioeconomic characteristics, psychosocial factors and migration conditions. Descriptive and multiple logistic regression analyses were conducted. RESULTS: The Spanish-born participants reported a better health status than the Latin America-born participants (79.8% versus 69.3%, p<0.001). Different patterns of self-reported health status were observed depending on the length of residence in the host country. The proportion of immigrants with a better health status is greater in those who have been in Spain for less than five years compared to those who have stayed longer. Better health status is significantly associated with being men, under 34 years old, being Spanish-born, having a monthly incomes of over 1000 euros, and having considerable social support and low stress. CONCLUSIONS: Better self-reported health status is associated with being Spanish-born, men, under 34 years old, having an uppermiddle-socioeconomic status, adequate social support, and low stress. Additionally, length of residence in the host country is seen as a related factor in the self-reported health status of immigrants

Antimicrobial resistance among migrants in Europe: a systematic review and meta-analysis

BACKGROUND: Rates of antimicrobial resistance (AMR) are rising globally and there is concern that increased migration is contributing to the burden of antibiotic resistance in Europe. However, the effect of migration on the burden of AMR in Europe has not yet been comprehensively examined. Therefore, we did a systematic review and meta-analysis to identify and synthesise data for AMR carriage or infection in migrants to Europe to examine differences in patterns of AMR across migrant groups and in different settings. METHODS: For this systematic review and meta-analysis, we searched MEDLINE, Embase, PubMed, and Scopus with no language restrictions from Jan 1, 2000, to Jan 18, 2017, for primary data from observational studies reporting antibacterial resistance in common bacterial pathogens among migrants to 21 European Union-15 and European Economic Area countries. To be eligible for inclusion, studies had to report data on carriage or infection with laboratory-confirmed antibiotic-resistant organisms in migrant populations. We extracted data from eligible studies and assessed quality using piloted, standardised forms. We did not examine drug resistance in tuberculosis and excluded articles solely reporting on this parameter. We also excluded articles in which migrant status was determined by ethnicity, country of birth of participants' parents, or was not defined, and articles in which data were not disaggregated by migrant status. Outcomes were carriage of or infection with antibiotic-resistant organisms. We used random-effects models to calculate the pooled prevalence of each outcome. The study protocol is registered with PROSPERO, number CRD42016043681. FINDINGS: We identified 2274 articles, of which 23 observational studies reporting on antibiotic resistance in 2319 migrants were included. The pooled prevalence of any AMR carriage or AMR infection in migrants was 25·4% (95% CI 19·1-31·8; I2 =98%), including meticillin-resistant Staphylococcus aureus (7·8%, 4·8-10·7; I2 =92%) and antibiotic-resistant Gram-negative bacteria (27·2%, 17·6-36·8; I2 =94%). The pooled prevalence of any AMR carriage or infection was higher in refugees and asylum seekers (33·0%, 18·3-47·6; I2 =98%) than in other migrant groups (6·6%, 1·8-11·3; I2 =92%). The pooled prevalence of antibiotic-resistant organisms was slightly higher in high-migrant community settings (33·1%, 11·1-55·1; I2 =96%) than in migrants in hospitals (24·3%, 16·1-32·6; I2 =98%). We did not find evidence of high rates of transmission of AMR from migrant to host populations. INTERPRETATION: Migrants are exposed to conditions favouring the emergence of drug resistance during transit and in host countries in Europe. Increased antibiotic resistance among refugees and asylum seekers and in high-migrant community settings (such as refugee camps and detention facilities) highlights the need for improved living conditions, access to health care, and initiatives to facilitate detection of and appropriate high-quality treatment for antibiotic-resistant infections during transit and in host countries. Protocols for the prevention and control of infection and for antibiotic surveillance need to be integrated in all aspects of health care, which should be accessible for all migrant groups, and should target determinants of AMR before, during, and after migration. FUNDING: UK National Institute for Health Research Imperial Biomedical Research Centre, Imperial College Healthcare Charity, the Wellcome Trust, and UK National Institute for Health Research Health Protection Research Unit in Healthcare-associated Infections and Antimictobial Resistance at Imperial College London