A first principles study of the electronic structure and optical response of heterobimetallic M-dicyanoaurate-based coordination polymers (M = Mn, Co, Ni, Zn and Cd).

The electronic structure and derived optical properties of five synthesized metal-dicyanoaurate(I), (K)M[Au(CN)2], (M = Mn, Co, Ni, Zn and Cd), coordination polymers are described from a combined experimental analysis and theoretical study based on density functional theory. In this sense, the topological features that influence the electronic structure, which in turn give rise to electronic transitions associated with the band gap energy, are studied from first principles calculations (with hybrid HSE06 and GGA-PBE density functionals) and electronic spectroscopy. The impact of gold (through spin-orbit coupling) and aurophilic interactions on the electronic transitions that gives rise to optical properties is described. The calculated projected density of states and band dispersion diagrams shed light on the molecular orbital distribution and the role of a dicyanoaurate(I) molecular block as the origin of the optical properties. Infrared, Raman and ultraviolet-visible spectroscopic analyses reveal the effect that charge transfer interactions, of a metal → ligand and metal → metal nature, have on the electronic behavior within the solids through association with the polarizing power of transition metals and gold atoms.

Electronic structure of graphene nanoribbons doped with nitrogen atoms: a theoretical insight.

The electronic structure of graphene nanoribbons doped with a graphitic type of nitrogen atoms has been studied using B3LYP, B2PLYP and CAS methods. In all but one case the restricted B3LYP solutions were unstable and the CAS calculations provided evidence for the multiconfigurational nature of the ground state with contributions from two dominant configurations. The relative stability of the doped nanoribbons depends mostly on the mutual position of the dopant atoms and notably less on the position of nitrogen atoms within the nanoribbon. N-graphitic doping affects cationic states much more than anionic ones due the participation of the nitrogen atoms in the stabilization of the positive charge, resulting in a drop in ionization energies (IPs) for N-graphitic doped systems. Nitrogen atoms do not participate in the negative charge stabilization of anionic species and, therefore, the doping does not affect the electron affinities (EAs). The unrestricted B3LYP method is the method of choice for the calculation of IPs and EAs. Restricted B3LYP and B2PLYP produces unreliable results for both IPs and EAs while CAS strongly underestimates the electron affinities. This is also true for the reorganization energies where restricted B3LYP produces qualitatively incorrect results. Doping changes the reorganization energy of the nanoribbons; the hole reorganization energy is generally higher than the corresponding electron reorganization energy due to the participation of nitrogen atoms in the stabilization of the positive charge.

Poverty-associated risk factors for wheezing in the first year of life in Honduras and El Salvador.

BACKGROUND: Risk factors for wheezing specifically during the first year of life have been studied in well-developed countries, but the information from developing countries is very scarce. There are no such studies focusing on factors derived from poverty. The aim of the present study was to determine if risk factors related to poverty are associated to wheezing during the first year of life in infants from Honduras and El Salvador. METHODS: A survey, using a validated questionnaire, was carried out in the metropolitan area of San Pedro Sula (Honduras) and in La Libertad (El Salvador) in centres where infants attended for a scheduled vaccination shot or a healthy child visit at 12 months of age. Fieldworkers offered questionnaires to parents and helped the illiterate when necessary. The main outcome variable was wheezing during the first year of life, as reported by parents. RESULTS: A total of 1047 infants in El Salvador and 780 in Honduras were included in the analysis. The prevalence of wheeze in the first year was higher in El Salvador (41.2%) than in Honduras (27.7%), as was recurrent wheezing defined as three or more episodes (18.4% vs. 11.7%). Wheezing and recurrent wheezing was associated to unpaved floor in the household (summary odds ratios for both countries 1.55, p=0.036 and 1.72, p=0.054 for any wheeze and recurrent wheezing, respectively); dust entering from streets (1.30, p=0.052 and 1.67, p=0.008); living in a heavily polluted area (1.33, p=0.037 and 1.52, p=0.033); and having mould stains on the household walls (1.36, p=0.072 and 1.76, p=0.007). Furthermore, marginal associations were found for additional person at home and use of kerosene as cooking fuel. University studies in the mother (0.34, p=0.046 and 0.32, p=0.022) and a professional occupation in the father (0.34, p=0.046 and 0.26, p=0.047) were associated to a lower risk. CONCLUSIONS: The prevalence of wheezing and recurrent wheezing is notoriously high in El Salvador and Honduras. In those populations factors related to poverty are associated to a higher prevalence of wheezing and recurrent wheezing, whereas higher maternal education and paternal professional occupation behave as protective factors.

Adsorptive separation of fructose and glucose from an agroindustrial waste of cashew industry.

Nearly all agroindustrial wastes have appreciable sugar content including cashew apples (Anacardium occidentale, L.), which are an important sub-utilized biomass source in Northeastern Brazil. Adsorption in fixed bed, both in batch and continuous modes, is a low-cost separation technique, which has been widely used in the concentration, separation and purification of bioproducts, such as sugars. The present work is an experimental study aimed at measuring responses in fixed bed, needed for design purposes. Two commercial ion-exchange resins were studied: DOWEX Monosphere 99/Ca and DIAION UBK555. The adsorbents showed linear isotherms for both sugars with marked selectivity for fructose (2.2 for DOWEX and 1.5 for DIAION). A mathematical model was used to estimate kinetic parameters and predict breakthrough behaviour of binary solutions and complex feeds. The kinetics of mass transfer was well described by a linear driving force approximation (LDF) and estimated kinetic constants were around 1 min(-1). The results indicate that the use of independent experiments with synthetic monocomponent solutions leads to reliable parameters, and the model is capable to foresee reasonably well the breakthrough curve of the sugars present in the juice, under different purification conditions. The use of complex feeds led to overshoot behaviour, possibly due to the irreversible adsorption of oligosaccharides.

Valoración aminérgica en pacientes con tumor hipofisiario productor de prolactina / Valoration aminergic in patients with hypophyseal prolactin producing tumors

Se estudia la importancia de las teorías etiológicas actuales de los tumores productores de prolactina (PRL). Así, los tumores productores de PRL pueden considerarse como un síndrome de múltiples etiologías, en las que participan diferentes estímulos peptidérgicos hipotalámicos. En pacientes con diagnóstico de tumor productor de PRL se estudiaron: A) la regulación dopaminérgica que estimula o inhibe la secreción de PRL, B) la neurotransmisión gabaminérgica que tambien estimula la secreción de PRL en el sistema nervioso central y lactotropo hipofisiario; y C) la vía serotoninérgica que produce liberación de PRL. Estos tipos de estímulos pueden ser la causa subyacente de la hiperplasia celular que origina la secreción de PRL .