989 resultados para sample covariance matrix


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This paper proposes a new feature representation method based on the construction of a Confidence Matrix (CM). This representation consists of posterior probability values provided by several weak classifiers, each one trained and used in different sets of features from the original sample. The CM allows the final classifier to abstract itself from discovering underlying groups of features. In this work the CM is applied to isolated character image recognition, for which several set of features can be extracted from each sample. Experimentation has shown that the use of CM permits a significant improvement in accuracy in most cases, while the others remain the same. The results were obtained after experimenting with four well-known corpora, using evolved meta-classifiers with the k-Nearest Neighbor rule as a weak classifier and by applying statistical significance tests.

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The synthesis of nano-sized ZIF-11 with an average size of 36 ± 6 nm is reported. This material has been named nano-zeolitic imidazolate framework-11 (nZIF-11). It has the same chemical composition and thermal stability and analogous H2 and CO2 adsorption properties to the conventional microcrystalline ZIF-11 (i.e. 1.9 ± 0.9 μm). nZIF-11 has been obtained following the centrifugation route, typically used for solid separation, as a fast new technique (pioneering for MOFs) for obtaining nanomaterials where the temperature, time and rotation speed can easily be controlled. Compared to the traditional synthesis consisting of stirring + separation, the reaction time was lowered from several hours to a few minutes when using this centrifugation synthesis technique. Employing the same reaction time (2, 5 or 10 min), micro-sized ZIF-11 was obtained using the traditional synthesis while nano-scale ZIF-11 was achieved only by using centrifugation synthesis. The small particle size obtained for nZIF-11 allowed the use of the wet MOF sample as a colloidal suspension stable in chloroform. This helped to prepare mixed matrix membranes (MMMs) by direct addition of the membrane polymer (polyimide Matrimid®) to the colloidal suspension, avoiding particle agglomeration resulting from drying. The MMMs were tested for H2/CO2 separation, improving the pure polymer membrane performance, with permeation values of 95.9 Barrer of H2 and a H2/CO2 separation selectivity of 4.4 at 35 °C. When measured at 200 °C, these values increased to 535 Barrer and 9.1.

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Mass-wasting deposits characterize the Upper Jurassic(?) to Lower Cretaceous sedimentary record of the Iberia Abyssal Plain. These deposits include olistostromes at Site 897, olistostromes and/or possible rock-fall deposits at Site 899, a breccia succession at Site 1068, slumped and fractured deposits at Site 1069, and a breccia succession at Site 1070. Whereas the exact origin of these deposits is uncertain, the regional common occurrence of middle to upper Mesozoic mass-wasting deposits suggests that they record the early rifting evolution of the west Iberia margin. This data report presents both qualitative and semiquantitative results from XRD analyses of the breccia matrix at Site 1068. In this study the matrix is defined as the fine-grained particles (as viewed through a binocular microscope) plus cement. Results are based on analytical methods that aimed to isolate the desired matrix from larger clast contamination prior to XRD analyses. In addition, the breccia was sampled at a higher resolution than was conducted aboard ship, producing a more complete description of downcore matrix mineralogical changes. The data presented here may be used to (1) further justify the subunit designation of Unit IV made aboard ship, (2) help determine to what degree the matrix and the larger clasts (studied in thin section aboard ship; Shipboard Scientific Party, 1998, doi:10.2973/odp.proc.ir.173.106.1998) are compositionally distinct, (3) help identify the extent of hydrothermal fluid migration in the breccia, and (4) support the proposed shipboard hypothesis that the Site 1068 breccia succession resulted from multiple mass-wasting.

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High-performance liquid chromatography coupled by an electrospray ion source to a tandem mass spectrometer (HPLC-EST-MS/ MS) is the current analytical method of choice for quantitation of analytes in biological matrices. With HPLC-ESI-MS/MS having the characteristics of high selectivity, sensitivity, and throughput, this technology is being increasingly used in the clinical laboratory. An important issue to be addressed in method development, validation, and routine use of HPLC-ESI-MS/MS is matrix effects. Matrix effects are the alteration of ionization efficiency by the presence of coeluting substances. These effects are unseen in the chromatograrn but have deleterious impact on methods accuracy and sensitivity. The two common ways to assess matrix effects are either by the postextraction addition method or the postcolumn infusion method. To remove or minimize matrix effects, modification to the sample extraction methodology and improved chromatographic separation must be performed. These two parameters are linked together and form the basis of developing a successful and robust quantitative HPLC-EST-MS/MS method. Due to the heterogenous nature of the population being studied, the variability of a method must be assessed in samples taken from a variety of subjects. In this paper, the major aspects of matrix effects are discussed with an approach to address matrix effects during method validation proposed. (c) 2004 The Canadian Society of Clinical Chemists. All rights reserved.

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Matrix application continues to be a critical step in sample preparation for matrix-assisted laser desorption/ionization (MALDI) mass spectrometry imaging (MSI). Imaging of small molecules such as drugs and metabolites is particularly problematic because the commonly used washing steps to remove salts are usually omitted as they may also remove the analyte, and analyte spreading is more likely with conventional wet matrix application methods. We have developed a method which uses the application of matrix as a dry, finely divided powder, here referred to as dry matrix application, for the imaging of drug compounds. This appears to offer a complementary method to wet matrix application for the MALDI-MSI of small molecules, with the alternative matrix application techniques producing different ion profiles, and allows the visualization of compounds not observed using wet matrix application methods. We demonstrate its value in imaging clozapine from rat kidney and 4-bromophenyl-1,4-diazabicyclo(3.2.2)nonane-4-carboxylic acid from rat brain. In addition, exposure of the dry matrix coated sample to a saturated moist atmosphere appears to enhance the visualization of a different set of molecules.

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Mass spectrometry imaging (MSI) is a powerful tool in metabolomics and proteomics for the spatial localization and identification of pharmaceuticals, metabolites, lipids, peptides and proteins in biological tissues. However, sample preparation remains a crucial variable in obtaining the most accurate distributions. Common washing steps used to remove salts, and solvent-based matrix application, allow analyte spreading to occur. Solvent-free matrix applications can reduce this risk, but increase the possibility of ionisation bias due to matrix adhesion to tissue sections. We report here the use of matrix-free MSI using laser desorption ionisation performed on a 12 T Fourier transform ion cyclotron resonance (FTICR) mass spectrometer. We used unprocessed tissue with no post-processing following thaw-mounting on matrix-assisted laser desorption ionisation (MALDI) indium-tin oxide (ITO) target plates. The identification and distribution of a range of phospholipids in mouse brain and kidney sections are presented and compared with previously published MALDI time-of-flight (TOF) MSI distributions.

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The present study investigates the effect of different sample preparation methods on the pyrolysis behaviour of metal-added biomass; Willow samples were compared in the presence of two salts of zinc and lead containing sulphate and nitrate anions which were added to the wood samples with three different techniques as dry-mixing, impregnation and ion-exchange. The effect of acid and water wash as common demineralisation pre-treatments were also analysed to evaluate their roles in the thermal degradation of the biomass. Results from thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR) and pyrolysis-mass spectrometry (Py-MS) measurements indicated that these pre-treatments change the matrix and the physical-chemical properties of wood. Results suggested that these structural changes increase the thermal stability of cellulose during pyrolysis. Sample preparation was also found to be a crucial factor during pyrolysis; different anions of metal salts changed the weight loss rate curves of wood material, which indicates changes in the primary degradation process of the biomass. Results also showed that dry-mixing, impregnation or ion-exchange influence the thermal behaviour of wood in different ways when a chosen metal salt was and added to the wood material. © 2011 Elsevier B.V. All rights reserved.

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Poly(β-hydroxybutyrate), (PHB), is a biologically produced, biodegradable thennoplastic with commercial potential. In this work the qualitative and quantitative investigations of the structure and degradation of a previously unstudied, novel, fibrous form of PHB, were completed. This gel-spun PHB fibrous matrix, PHB(FM), which has a similar appearance to cotton wool, possesses a relatively complex structure which combines a large volume with a low mass and has potential for use as a wound scaffolding device. As a result of the intrinsic problems presented by this novel structure, a new experimental procedure was developed to analyze the degradation of the PHB to its monomer hydroxybutyric acid, (HBA). This procedure was used in an accelerated degradation model which accurately monitored the degradation of the undegraded and degraded fractions of a fibrous matrix and the degradation of its PHB component. The in vitro degradation mechanism was also monitored using phase contrast and scanning electron microscopy, differential scanning calorimetry, fibre diameter distributions and Fourier infra-red photoacoustic spectroscopy. The accelerated degradation model was used to predict the degradation of the samples in the physiological model and this provided a clearer picture as to the samples potential biodegradation as medical implantation devices. The degradation of the matrices was characterized by an initial penetration of the degradative medium and weakening of the fibre integrity due to cleavage of the ester linkages, this then led to the physical collapse of the fibres which increased the surface area to volume ratio of the sample and facilitated its degradation. Degradation in the later stages was reduced due to the experimental kinetics, compaction and degradation resistant material, most probably the highly crystalline regions of the PHB. The in vitro degradation of the PHB(FM) was influenced by blending with various polysaccharides, copolymerizing with poly(~-hydroxyvalerate), (PHV), and changes to the manufacturing process. The degradation was also detennined to be faster than that of conventional melt processed PHB based samples. It was concluded that the material factors such as processing, sample size and shape affected the degradation of PHB based samples with the major factor of sample surface area to volume ratio being of paramount importance in determining the degradation of a sample.

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In this paper we discuss a fast Bayesian extension to kriging algorithms which has been used successfully for fast, automatic mapping in emergency conditions in the Spatial Interpolation Comparison 2004 (SIC2004) exercise. The application of kriging to automatic mapping raises several issues such as robustness, scalability, speed and parameter estimation. Various ad-hoc solutions have been proposed and used extensively but they lack a sound theoretical basis. In this paper we show how observations can be projected onto a representative subset of the data, without losing significant information. This allows the complexity of the algorithm to grow as O(n m 2), where n is the total number of observations and m is the size of the subset of the observations retained for prediction. The main contribution of this paper is to further extend this projective method through the application of space-limited covariance functions, which can be used as an alternative to the commonly used covariance models. In many real world applications the correlation between observations essentially vanishes beyond a certain separation distance. Thus it makes sense to use a covariance model that encompasses this belief since this leads to sparse covariance matrices for which optimised sparse matrix techniques can be used. In the presence of extreme values we show that space-limited covariance functions offer an additional benefit, they maintain the smoothness locally but at the same time lead to a more robust, and compact, global model. We show the performance of this technique coupled with the sparse extension to the kriging algorithm on synthetic data and outline a number of computational benefits such an approach brings. To test the relevance to automatic mapping we apply the method to the data used in a recent comparison of interpolation techniques (SIC2004) to map the levels of background ambient gamma radiation. © Springer-Verlag 2007.

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The morphology, chemical composition, and mechanical properties in the surface region of α-irradiated polytetrafluoroethylene (PTFE) have been examined and compared to unirradiated specimens. Samples were irradiated with 5.5 MeV 4He2+ ions from a tandem accelerator to doses between 1 × 106 and 5 × 1010 Rad. Static time-of-flight secondary ion mass spectrometry (ToF-SIMS), using a 20 keV C60+ source, was employed to probe chemical changes as a function of a dose. Chemical images and high resolution spectra were collected and analyzed to reveal the effects of a particle radiation on the chemical structure. Residual gas analysis (RGA) was utilized to monitor the evolution of volatile species during vacuum irradiation of the samples. Scanning electron microscopy (SEM) was used to observe the morphological variation of samples with increasing a particle dose, and nanoindentation was engaged to determine the hardness and elastic modulus as a function of a dose. The data show that PTFE nominally retains its innate chemical structure and morphology at a doses <109 Rad. At α doses ≥109 Rad the polymer matrix experiences increased chemical degradation and morphological roughening which are accompanied by increased hardness and declining elasticity. At  α doses >1010 Rad the polymer matrix suffers severe chemical degradation and material loss. Chemical degradation is observed in ToF-SIMS by detection of ions that are indicative of fragmentation, unsaturation, and functionalization of molecules in the PTFE matrix. The mass spectra also expose the subtle trends of crosslinking within the α-irradiated polymer matrix. ToF-SIMS images support the assertion that chemical degradation is the result of a particle irradiation and show morphological roughening of the sample with increased a dose. High resolution SEM images more clearly illustrate the morphological roughening and the mass loss that accompanies high doses of a particles. RGA confirms the supposition that the outcome of chemical degradation in the PTFE matrix with continuing irradiation is evolution of volatile species resulting in morphological roughening and mass loss. Finally, we reveal and discuss relationships between chemical structure and mechanical properties such as hardness and elastic modulus.

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The environmental dynamics of dissolved organic matter (DOM) were characterized for a shallow, subtropical, seagrass-dominated estuarine bay, namely Florida Bay, USA. Large spatial and seasonal variations in DOM quantity and quality were assessed using dissolved organic C (DOC) measurements and spectrophotometric properties including excitation emission matrix (EEM) fluorescence with parallel factor analysis (PARAFAC). Surface water samples were collected monthly for 2 years across the bay. DOM characteristics were statistically different across the bay, and the bay was spatially characterized into four basins based on chemical characteristics of DOM as determined by EEM-PARAFAC. Differences between zones were explained based on hydrology, geomorphology, and primary productivity of the local seagrass community. In addition, potential disturbance effects from a very active hurricane season were identified. Although the overall seasonal patterns of DOM variations were not significantly affected on a bay-wide scale by this disturbance, enhanced freshwater delivery and associated P and DOM inputs (both quantity and quality) were suggested as potential drivers for the appearance of algal blooms in high impact areas. The application of EEM-PARAFAC proved to be ideally suited for studies requiring high sample throughput methods to assess spatial and temporal ecological drivers and to determine disturbance-induced impacts in aquatic ecosystems.