117 resultados para OXIDATION POTENTIALS
Resumo:
Event-related brain potentials (ERP) are important neural correlates of cognitive processes. In the domain of language processing, the N400 and P600 reflect lexical-semantic integration and syntactic processing problems, respectively. We suggest an interpretation of these markers in terms of dynamical system theory and present two nonlinear dynamical models for syntactic computations where different processing strategies correspond to functionally different regions in the system's phase space.
Resumo:
We investigated whether it is possible to control the temporal window of attention used to rapidly integrate visual information. To study the underlying neural mechanisms, we recorded ERPs in an attentional blink task, known to elicit Lag-1 sparing. Lag-1 sparing fosters joint integration of the two targets, evidenced by increased order errors. Short versus long integration windows were induced by showing participants mostly fast or slow stimuli. Participants expecting slow speed used a longer integration window, increasing joint integration. Difference waves showed an early (200 ms post-T2) negative and a late positive modulation (390 ms) in the fast group, but not in the slow group. The modulations suggest the creation of a separate event for T2, which is not needed in the slow group, where targets were often jointly integrated. This suggests that attention can be guided by global expectations of presentation speed within tens of milliseconds.
Resumo:
The study of motor unit action potential (MUAP) activity from electrornyographic signals is an important stage on neurological investigations that aim to understand the state of the neuromuscular system. In this context, the identification and clustering of MUAPs that exhibit common characteristics, and the assessment of which data features are most relevant for the definition of such cluster structure are central issues. In this paper, we propose the application of an unsupervised Feature Relevance Determination (FRD) method to the analysis of experimental MUAPs obtained from healthy human subjects. In contrast to approaches that require the knowledge of a priori information from the data, this FRD method is embedded on a constrained mixture model, known as Generative Topographic Mapping, which simultaneously performs clustering and visualization of MUAPs. The experimental results of the analysis of a data set consisting of MUAPs measured from the surface of the First Dorsal Interosseous, a hand muscle, indicate that the MUAP features corresponding to the hyperpolarization period in the physisiological process of generation of muscle fibre action potentials are consistently estimated as the most relevant and, therefore, as those that should be paid preferential attention for the interpretation of the MUAP groupings.
Resumo:
The identification and visualization of clusters formed by motor unit action potentials (MUAPs) is an essential step in investigations seeking to explain the control of the neuromuscular system. This work introduces the generative topographic mapping (GTM), a novel machine learning tool, for clustering of MUAPs, and also it extends the GTM technique to provide a way of visualizing MUAPs. The performance of GTM was compared to that of three other clustering methods: the self-organizing map (SOM), a Gaussian mixture model (GMM), and the neural-gas network (NGN). The results, based on the study of experimental MUAPs, showed that the rate of success of both GTM and SOM outperformed that of GMM and NGN, and also that GTM may in practice be used as a principled alternative to the SOM in the study of MUAPs. A visualization tool, which we called GTM grid, was devised for visualization of MUAPs lying in a high-dimensional space. The visualization provided by the GTM grid was compared to that obtained from principal component analysis (PCA). (c) 2005 Elsevier Ireland Ltd. All rights reserved.
Resumo:
This paper outlines a method for automatic artefact removal from multichannel recordings of event-related potentials (ERPs). The proposed method is based on, firstly, separation of the ERP recordings into independent components using the method of temporal decorrelation source separation (TDSEP). Secondly, the novel lagged auto-mutual information clustering (LAMIC) algorithm is used to cluster the estimated components, together with ocular reference signals, into clusters corresponding to cerebral and non-cerebral activity. Thirdly, the components in the cluster which contains the ocular reference signals are discarded. The remaining components are then recombined to reconstruct the clean ERPs.
Resumo:
Low-energy and photoemission electron microscopy enables the determination of facet planes of polycrystalline surfaces and the study of their chemical composition at the sub-m scale. Using these techniques the early oxidation stages of nickel were studied. After exposing the surface to 20 L of oxygen at 373 K a uniform layer of chemisorbed oxygen was found on all facets. After oxygen exposure at 473–673 K, small NiO crystallites are formed on all facets but not in the vicinity of all grain boundaries. The crystallites are separated by areas of bare Ni without significant oxygen coverage.
Resumo:
We present a comparative study between LC/MALDI/MS/MS and LC/ESI/MS/MS. Diagnostic biomarkers in saliva have been identified for monitoring caries, periodontitis, oral cancer, salivary gland diseases, and systemic disorders e.g. hepatitis and HIV[1]. Saliva is similar to serum in that there are a small number of highly abundant proteins and many low abundance proteins. There are 35 previously identified salivary proteins [1-4]. We prepared a representative sample of cysteine containing peptides and oxidised them to improve their fragmentation under MALDI conditions. In total 20 proteins were identified with 6 been identified by both methods. Surprisingly there was little overlap in the peptides used to identify the proteins between the two methods
Resumo:
Methane is the second most important anthropogenic greenhouse gas in the atmosphere next to carbon dioxide. Its global warming potential (GWP) for a time horizon of 100 years is 25, which makes it an attractive target for climate mitigation policies. Although the methane GWP traditionally includes the methane indirect effects on the concentrations of ozone and stratospheric water vapour, it does not take into account the production of carbon dioxide from methane oxidation. We argue here that this CO2-induced effect should be included for fossil sources of methane, which results in slightly larger GWP values for all time horizons. If the global temperature change potential is used as an alternative climate metric, then the impact of the CO2-induced effect is proportionally much larger. We also discuss what the correction term should be for methane from anthropogenic biogenic sources.
Resumo:
We present a kinetic double layer model coupling aerosol surface and bulk chemistry (K2-SUB) based on the PRA framework of gas-particle interactions (Poschl-Rudich-Ammann, 2007). K2-SUB is applied to a popular model system of atmospheric heterogeneous chemistry: the interaction of ozone with oleic acid. We show that our modelling approach allows de-convoluting surface and bulk processes, which has been a controversial topic and remains an important challenge for the understanding and description of atmospheric aerosol transformation. In particular, we demonstrate how a detailed treatment of adsorption and reaction at the surface can be coupled to a description of bulk reaction and transport that is consistent with traditional resistor model formulations. From literature data we have derived a consistent set of kinetic parameters that characterise mass transport and chemical reaction of ozone at the surface and in the bulk of oleic acid droplets. Due to the wide range of rate coefficients reported from different experimental studies, the exact proportions between surface and bulk reaction rates remain uncertain. Nevertheless, the model results suggest an important role of chemical reaction in the bulk and an approximate upper limit of similar to 10(-11) cm(2) s(-1) for the surface reaction rate coefficient. Sensitivity studies show that the surface accommodation coefficient of the gas-phase reactant has a strong non-linear influence on both surface and bulk chemical reactions. We suggest that K2-SUB may be used to design, interpret and analyse future experiments for better discrimination between surface and bulk processes in the oleic acid-ozone system as well as in other heterogeneous reaction systems of atmospheric relevance.
Resumo:
The syntheses and characterizations of several complexes containing ferrocenylethynyl and ferrocene-1,1'-bis(ethynyl) groups attached to M(PP)Cp'[M = Fe, Ru, PP = dppe, Cp'= Cp*; M = Ru, Os, PP = (PPh3)(2), dppe, Cp' = Cp] are described. Reactions with tetracyanoethene have given either tetracyanobuta-1,3-dienyl or eta(3)-allylic derivatives, while addition of Me+ afforded the corresponding vinylidene derivatives. Some electrochemical measurements are discussed in terms of electronic communication between the redox-active M(PP)Cp' groups through the ferrocene nucleus. The molecular structures of 14 of these complexes have been determined by crystallographic methods.
Resumo:
We present a novel kinetic multi-layer model that explicitly resolves mass transport and chemical reaction at the surface and in the bulk of aerosol particles (KM-SUB). The model is based on the PRA framework of gas-particle interactions (Poschl-Rudich-Ammann, 2007), and it includes reversible adsorption, surface reactions and surface-bulk exchange as well as bulk diffusion and reaction. Unlike earlier models, KM-SUB does not require simplifying assumptions about steady-state conditions and radial mixing. The temporal evolution and concentration profiles of volatile and non-volatile species at the gas-particle interface and in the particle bulk can be modeled along with surface concentrations and gas uptake coefficients. In this study we explore and exemplify the effects of bulk diffusion on the rate of reactive gas uptake for a simple reference system, the ozonolysis of oleic acid particles, in comparison to experimental data and earlier model studies. We demonstrate how KM-SUB can be used to interpret and analyze experimental data from laboratory studies, and how the results can be extrapolated to atmospheric conditions. In particular, we show how interfacial and bulk transport, i.e., surface accommodation, bulk accommodation and bulk diffusion, influence the kinetics of the chemical reaction. Sensitivity studies suggest that in fine air particulate matter oleic acid and compounds with similar reactivity against ozone (carbon-carbon double bonds) can reach chemical lifetimes of many hours only if they are embedded in a (semi-)solid matrix with very low diffusion coefficients (< 10(-10) cm(2) s(-1)). Depending on the complexity of the investigated system, unlimited numbers of volatile and non-volatile species and chemical reactions can be flexibly added and treated with KM-SUB. We propose and intend to pursue the application of KM-SUB as a basis for the development of a detailed master mechanism of aerosol chemistry as well as for the derivation of simplified but realistic parameterizations for large-scale atmospheric and climate models.