Ethanol Oxidation Reaction Mechanism on Gold Nanowires from Density Functional Theory.

Thin gold nanowires (NWs) are materials that could be used as support in different chemical reactions. Using density functional theory (DFT) it was shown that NWs that form linear atomic chains (LACs) are suitable for stimulating chemical reactions. To this end, the oxidation reaction of ethanol supported on the LACs of Au-NWs was investigated. Two types of LACs were used for the study, one pure and the other with an oxygen impurity. The results showed that the oxygen atom in the LAC fulfills important functions throughout the reaction pathway. Before the chemical reaction, it was observed that the LAC with impurity gains structural stability, that is, the oxygen acts as an anchor for the gold atoms in the LAC. In addition, the LAC was shown to be sensitive to disturbances in its vicinity, which modifies its nucleophilic character. During the chemical reaction, the oxidation of ethanol occurs through two different reaction paths and in two stages, both producing acetaldehyde (CH3 CHO). The different reaction pathways are a consequence of the presence of oxygen in the LAC (oxygen conditions the formation of reaction intermediates). In addition, the oxygen in the LAC also modifies the kinetic behavior in both reaction stages. It was observed that, by introducing an oxygen impurity in the LAC, the activation energy barriers decrease ∼69 % and ∼97 % in the first and second reaction stages, respectively.

Bilateral Acute Depigmentation of the Iris (BADI) following Covid-19 Infection.

PURPOSE: To present a case of bilateral acute iris depigmentation after covid 19 infection. CASE REPORT: A 55-year-old female presented with binocular pain and blurred vision a month after being diagnosed with severe acute respiratory syndrome - coronavirus-2 (SARS-CoV-2). She presented pigment dispersion in the anterior chamber and pigment depositions on the corneal endothelium. The patient was treated with dexamethasone and during follow-up visits, the pigment dispersion decreased and the symptoms ceased. CONCLUSIONS: Covid-19 infection may be associated with rare ocular disorders such as BADI.

Analytical and numerical study of the non-linear noisy voter model on complex networks.

We study the noisy voter model using a specific non-linear dependence of the rates that takes into account collective interaction between individuals. The resulting model is solved exactly under the all-to-all coupling configuration and approximately in some random network environments. In the all-to-all setup, we find that the non-linear interactions induce bona fide phase transitions that, contrary to the linear version of the model, survive in the thermodynamic limit. The main effect of the complex network is to shift the transition lines and modify the finite-size dependence, a modification that can be captured with the introduction of an effective system size that decreases with the degree heterogeneity of the network. While a non-trivial finite-size dependence of the moments of the probability distribution is derived from our treatment, mean-field exponents are nevertheless obtained in the thermodynamic limit. These theoretical predictions are well confirmed by numerical simulations of the stochastic process.

Síndrome de piernas inquietas e hipotiroidismo / Restless legs syndrome and hypothyroidism

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Fragmentation transition in a coevolving network with link-state dynamics.

We study a network model that couples the dynamics of link states with the evolution of the network topology. The state of each link, either A or B, is updated according to the majority rule or zero-temperature Glauber dynamics, in which links adopt the state of the majority of their neighboring links in the network. Additionally, a link that is in a local minority is rewired to a randomly chosen node. While large systems evolving under the majority rule alone always fall into disordered topological traps composed by frustrated links, any amount of rewiring is able to drive the network to complete order, by relinking frustrated links and so releasing the system from traps. However, depending on the relative rate of the majority rule and the rewiring processes, the system evolves towards different ordered absorbing configurations: either a one-component network with all links in the same state or a network fragmented in two components with opposite states. For low rewiring rates and finite-size networks there is a domain of bistability between fragmented and nonfragmented final states. Finite-size scaling indicates that fragmentation is the only possible scenario for large systems and any nonzero rate of rewiring.

Dynamics of link states in complex networks: the case of a majority rule.

Motivated by the idea that some characteristics are specific to the relations between individuals and not to the individuals themselves, we study a prototype model for the dynamics of the states of the links in a fixed network of interacting units. Each link in the network can be in one of two equivalent states. A majority link-dynamics rule is implemented, so that in each dynamical step the state of a randomly chosen link is updated to the state of the majority of neighboring links. Nodes can be characterized by a link heterogeneity index, giving a measure of the likelihood of a node to have a link in one of the two states. We consider this link-dynamics model in fully connected networks, square lattices, and Erdös-Renyi random networks. In each case we find and characterize a number of nontrivial asymptotic configurations, as well as some of the mechanisms leading to them and the time evolution of the link heterogeneity index distribution. For a fully connected network and random networks there is a broad distribution of possible asymptotic configurations. Most asymptotic configurations that result from link dynamics have no counterpart under traditional node dynamics in the same topologies.

Update rules and interevent time distributions: slow ordering versus no ordering in the voter model.

We introduce a general methodology of update rules accounting for arbitrary interevent time (IET) distributions in simulations of interacting agents. We consider in particular update rules that depend on the state of the agent, so that the update becomes part of the dynamical model. As an illustration we consider the voter model in fully connected, random, and scale-free networks with an activation probability inversely proportional to the time since the last action, where an action can be an update attempt (an exogenous update) or a change of state (an endogenous update). We find that in the thermodynamic limit, at variance with standard updates and the exogenous update, the system orders slowly for the endogenous update. The approach to the absorbing state is characterized by a power-law decay of the density of interfaces, observing that the mean time to reach the absorbing state might be not well defined. The IET distributions resulting from both update schemes show power-law tails.

Electronic structure and optical spectra of catechol on TiO2 nanoparticles from real time TD-DFT simulations.

The electronic structure and the optical response of free catechol, [Ti(cat)(3)](2-) complex, and catechol bound to TiO(2) nanoclusters have been analysed using time dependent density functional theory (TD-DFT) performing calculations both in real time and frequency domains. Both approaches lead to similar results providing the basis sets and functionals are similar. For all cases, the simulated spectra agree well with the experimental ones. For the adsorption systems, the spectra show a band at 4.7 eV associated to intramolecular catechol π→π* transitions, and low energy bands corresponding to transitions from catechol to the cluster with a tail that is red-shifted when the coupling between the dye and the cluster is more effective. Thus, dissociative adsorption modes provide longer tails than the molecular mode. Although the bidentate complex is more stable than the monodentate, the energy difference between both is smaller when the cluster size increases. Small cluster models reproduce the main features of the optical response, however, the (TiO(2))(15) cluster constitutes the minimal size to provide a complete picture. In this case, the conventional TD-DFT (frequency domain) calculations are highly demanding computationally, while real time TD-DFT is more efficient and the calculations become affordable.

Chemical reactions in 2D: self-assembly and self-esterification of 9(10),16-dihydroxypalmitic acid on mica surface.

9(10),16-Dihydroxypalmitic acid (diHPA) is a particularly interesting polyhydroxylated fatty acid (1) because it is the main monomer of cutin, the most abundant biopolyester in nature, and (2) because the presence of a terminal and a secondary hydroxyl group in midchain positions provides an excellent model to study their intermolecular interactions in a confined phase such as self-assembled layers. In this study we have combined atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), attenuated total reflection Fourier transform infrared (ATR-FT-IR) spectroscopy, as well as molecular dynamics (MD) simulations to conclude that the self-assembling of diHPA molecules on mica is a layer by layer process following a Brunauer-Emmett-Teller (BET) type isotherm and with the first layer growing much faster than the rest. Interactions between secondary hydroxyls reinforce the cohesive energy of the monolayer, while the presence of the terminal hydroxyl group is necessary to trigger the multilayered growth. Besides, XPS and ATR-FT-IR spectroscopies clearly indicate that spontaneous self-esterification occurs upon self-assembling. The esterification reaction is a prerequisite to propose a self-assembly route for the biosynthesis of cutin in nature. Molecular dynamics simulations have shown that internal molecular reorganization within the self-assembled layers provides the appropriate intermolecular orientation to facilitate the nucleophilic attack and the release of a water molecule required by the esterification reaction.

Broad lifetime distributions for ordering dynamics in complex networks.

We search for conditions under which a characteristic time scale for ordering dynamics toward either of two absorbing states in a finite complex network of interactions does not exist. With this aim, we study random networks and networks with mesoscale community structure built up from randomly connected cliques. We find that large heterogeneity at the mesoscale level of the network appears to be a sufficient mechanism for the absence of a characteristic time for the dynamics. Such heterogeneity results in dynamical metastable states that survive at any time scale.

Conjunctivitis and Total IgE in Lacrimal Fluid: Lacrytest Screening.

Total tear IgE has been considered to play an important role in allergic conjunctivitis, and measurement has been considered useful for diagnosis. The aim of this study was to ascertain whether Lacrytest(®), a new commercialised method to detect IgE levels in lacrimal fluid, could constitute a screening test for the diagnosis of allergic conjunctivitis. This was a cross-sectional study. Patients with seasonal and perennial allergic conjunctivitis, vernal keratoconjunctivitis and a control group were included. Clinical history, ophthalmic examination, skin prick test and conjunctival provocation test were obtained. Lacrytest(®) was later performed in all groups. Fifty-four patients were enrolled: thirty with IgE-mediated conjunctivitis and, nine with vernal keratoconjunctivitis and fifteen controls. Lacrytest(®) was negative in all controls, positive in 20% of the IgE-mediated conjunctivitis group and in 88.9% of the vernal keratoconjunctivitis group. Global statistically-significant differences were found among the three groups (P = .003). Sensitivity of the test in the IgE-mediated conjunctivitis group was 20%, specificity 100%, positive predictive value 100%, and negative predictive value 38.46%, while in VKC sensitivity was 88.88%, specificity 100%, positive predictive value 100%, and negative predictive value 93.75%. Our data confirm that this test is not useful for screening allergic conjunctivitis. Lacrytest(®), while not providing any useful information to an allergist, could be helpful for ophthalmologists to confirm an IgE-mediated or VKC conjunctivitis.

Aneurisma congénito del ductus arterioso: a propósito de un caso con revisión de la literatura / Congenital aneurisma of a patent ductos arterious: a case report

Presentamos un caso de aneurisma congénito del ductus arteriosos con insuficiencia cardiaca neonatal e imagen de masa paracardíaca izquierda en la radiografía de tórax, diagnosticado mediante ecocardiografía y confirmado con angiografía. La paciente fue intervenida sin complicaciones, realizándose exéresis del aneurisma y cierre del ductus. En la evolución se diagnosticó de síndrome de Beals-Hetch. Tras seis años de seguimiento, la paciente está asintomática y con normalidad cardiovascular determinada por ecocardiografía (AU)

We report a case of aneurysm of the ductus arteriosus present with heart failure in the neonatal period. The chest x-ray showed an enlarged heart together with a left paracardiac mass. The echocardiogram showed an aneurysmatic patent ductus arteriosus, confirmed by angiography. The condition was successfully corrected by surgery without complications. In the follow-up a Beals-Hetch syndrome was diagnosed. After 6 years of follow-up, the patient remains symptoms free with normal echocardiographic data (AU)

Influence of temperature on the interaction between Pd clusters and the TiO2 (110) surface.

The behavior of a Pd nanocluster on the rutile TiO2 (110) surface has been analyzed by extensive first principles molecular dynamics simulations between 100 K and 1073 K. Calculations predict a steep change in the morphological and electronic cluster structure around 800 K in excellent agreement with previous experimental evidence. At low temperature, the cluster geometry is mainly controlled by the substrate structure; however, upon the transition temperature, the cluster-substrate interaction decreases appreciably, and the cluster adopts a geometry more stable in vacuum and becomes metallic. These results illustrate at an atomistic level the influence of temperature on the geometrical and electronic properties of oxide-supported clusters.

Ba adsorption on the stoichiometric and defective TiO(2) (110) surface from first-principles calculations.

A theoretical study on Ba adsorption on the rutile TiO(2) (110) surface has been carried out by means of plane-wave, plane augmented waves potential, density functional theory calculations. A model consisting on a (4 x 1) unit cell, which corresponds to coverage of 0.125 monolayer (ML), has been used and several potential adsorption sites on the stoichiometric surface have been tried. It has been found that the most stable site is with the Ba atom in a position where it is bound to two bridging oxygen atoms and an in-plane oxygen atom forming equivalent bonds (OB site). The adsorption energy is 0.71 eV referred to the formation of Ba bulk and is about 0.3 eV more stable than other adsorption sites. The Ba-surface interaction produces some surface relaxation in all cases. The OB site is stable at moderate temperatures; however, after extensive molecular dynamic calculations it is found that atoms diffuse on the surface by means of a jumping mechanism among several stable positions. The presence of bridging oxygen vacancies does not alter significantly this picture since the adsorption close to defects is not energetically favorable and the atoms tend to move away from vacancies. A strong covalent character has been found in the nature of the bonding, which contrasts with previous suggestions of the existence of Ba(2+) species on the surface. When the coverage is increased to 0.25 ML by adding a Ba atom to the supercell, there is a significant repulsion between Ba atoms that move away from each other to occupy OB sites. Thus, the adsorption energy values per atom diminish. For the stoichiometric surface two equivalent adsorption patterns are found, whereas only one is found for the defective surface.

Local versus global interactions in nonequilibrium transitions: A model of social dynamics.

A nonequilibrium system of locally interacting elements in a lattice with an absorbing order-disorder phase transition is studied under the effect of additional interacting fields. These fields are shown to produce interesting effects in the collective behavior of this system. Both for autonomous and external fields, disorder grows in the system when the probability of the elements to interact with the field is increased. There exists a threshold value of this probability beyond which the system is always disordered. The domain of parameters of the ordered regime is larger for nonuniform local fields than for spatially uniform fields. However, the zero field limit is discontinous. In the limit of vanishingly small probability of interaction with the field, autonomous or external fields are able to order a system that would fall in a disordered phase under local interactions of the elements alone. We consider different types of fields which are interpreted as forms of mass media acting on a social system in the context of Axelrod's model for cultural dissemination.

Food-drug interactions in the summary of product characteristics of proprietary medicinal products.

BACKGROUND: Food-drug interactions can produce negative effects in the safety and efficacy of drug therapy, as well as in the nutritional status of the patient. However, the data commonly provided to the prescriber about possible nutrient-pharmacological compound interactions and the recommendations for their prevention are often scarce. The summary of product characteristics (SmPC) of a proprietary medicinal product, as authorised by the health authorities in Europe, is usually the main source of information for the health professional. Therefore, the SmPC can be a useful tool to prevent or reduce food-drug interactions and, as a consequence, improve the therapeutical approach. OBJECTIVE: The aim of this study was to assess the information about food-drug interactions with potential clinical relevance as it is described in the SmPCs of the authorised medicinal products in a European Union country (Spain). METHODS: A bibliographical search of food-drug interactions, including nutrients and alcohol, was carried out. The adequate information to be included in the SmPC was defined in accordance with the European Recommendations in this field. The SmPCs of the medicinal products containing selected active substances were examined with emphasis on food-drug interactions. RESULTS: It was found that, frequently, the information concerning food-drug interactions as is mentioned in the SmPC of the authorised medicinal products in Spain does not fulfil the current recommendations, both in quantity and quality. Indeed, the available data reveal that the food-drug information is only mentioned in 72.7% of all SmPC where it should be and it was only found in the specific section for interactions in 36.0% of all cases. The description and agreement with recommendations for each SmPC item ranged between 4.2% and 36.0% and between 31.8% and 49.0%, respectively. Some related factors, such as the clinical relevance of the interaction, the existence of an authorised SmPC and the registration procedure followed, influence the information characteristics concerning food-drug interactions. CONCLUSION: The SmPC is a suboptimal source of information for food-drug interactions.

Oxygen vacancies on TiO2 (110) from first principles calculations.

We have carried out a systematic study of oxygen vacancy formation on the TiO2 (110) surface by means of plane-wave pseudopotential density-functional theory calculations. We have used models with the mean number of vacancies per surface unit cell being theta=0.25 and theta=0.5. The study comprises several kind of vacancies within the outermost layers of the surface. The use of a suitable set of technical parameter is often essential in order to get accurate results. We find that the presence of bridging vacancies is energetically favored in accordance to experimental data, although the formation of sub-bridging vacancies might be possible at moderate temperatures. Surprisingly, the spin state of the vacancy has little influence on the results. Atomic displacements are also analyzed and found to be strongly dependent on the particular arrangement of vacancies.

Effects of specific immunotherapy on the development of new sensitisations in monosensitised patients.

BACKGROUND: Specific immunotherapy (SIT) is the only treatment that interferes with the basic pathophysiological mechanisms of allergic disease and is widely used in the management of clinically significant respiratory IgE-mediated diseases. Nevertheless, until recently, information on the influence of SIT on the development of new allergic sensitisations has been scant. METHODS: One hundred consecutive patients (45 males and 55 females, aged 6 to 69 years) with respiratory allergic diseases and attending the allergy unit of a general hospital were selected. All had been diagnosed by clinical history and skin prick tests of allergic rhinitis and/or asthma, were monosensitised (71 to Dermatophagoides spp, 22 to Parietaria judaica pollen and 7 to grass pollen) and had been followed up as outpatients between 1990-98. Sixty-six patients had been treated with conventional SIT for at least 3 years, while thirty-four followed only environmental measures and drug treatment. Family atopy status (first-degree relatives), smoking, family pets (cat and/or dog), rhinitis and/or asthma symptom score and inhalant skin prick tests to the same aeroallergens were compared between baseline and after 3 to 5 years of treatment. RESULTS: No statistically-significant differences in the development of new sensitisations were observed between the two groups (36.4 % of SIT-treated patients versus 38.2 % in control group, RR = 0.97, CI 95 %: 0.72-1.3). Smoking, family atopy history and pets did not appear to be risk factors for the development of neosensitisations (p < 0.05). Nevertheless, SIT-treated patients presented a better clinical score than the control group, with improvements of 89.4 % and 61.8 %, respectively (p = 0.007). CONCLUSIONS: Three-year SIT did not protect against development of new sensitisations in monosensitised allergic rhinitis or asthma. Smoking, family atopy history and pets were not associated with development of new sensitisations. Clinical score improved significantly in the SIT-treated group compared with drug-treated patients.