Estudo da reação entre o metanol e o acetato de etila em catalisadores Mg/La por espectroscopia no infravermelho acoplada a espectrometria de massas

A transesterificação metílica em meio homogêneo é catalisada por bases, tais como hidróxidos e alcóxidos de sódio ou potássio e se processa em baixa temperatura de reação, mesmo em escala industrial. A utilização de catalisadores formados por sólidos básicos aparece como uma alternativa promissora aos processos homogêneos convencionais, tendo em vista as inúmeras vantagens como a redução da ocorrência das reações indesejáveis de saponificação e redução de custos dos processos pela diminuição do número de operações associadas. Em estudos anteriores realizados pelo grupo, catalisadores a base de Mg/La com diferentes composições químicas (9:1, 1:1 e 1:9) mostraram-se promissores para a obtenção de ésteres metílicos via reação de transesterificação, porém não foi possível fazer uma correlação entre atividade catalítica e as propriedades físico-químicas quando toda a série foi considerada. Assim, a realização de um estudo de caráter fundamental, baseado em reações modelo e uso de moléculas sonda, permite avançar no entendimento das propriedades de superfície destes catalisadores. Portanto, o presente trabalho estuda a reação entre metanol e acetato de etila em catalisadores a base de Mg/La utilizando espectroscopia de reflectância difusa no infravermelho com transformada de Fourier (DRIFTS) acoplada a espectrometria de massas (MS) identificando os intermediários e produtos formados para determinar a rota reacional. As análises de difração de raios X mostram que os precursores são predominantemente compostos por carbonatos hidratados de magnésio (Mg/La 1:1 e 9:1) e de lantânio (Mg/La 1:9). Os perfis de decomposição térmica e difratogramas de raios X obtidos a partir de tratamento térmico in situ indicaram que estes carbonatos se decompõem apenas a partir de 750 C. As análises de Dessorção a Temperatura Programada realizadas com moléculas sonda, metanol e acetato de etila, mostraram a adsorção em maior quantidade do metanol independente da composição química do sólido. A partir dos resultados obtidos por DRIFTS-MS foi proposta uma rota reacional para a reação de transesterificação do acetato de etila e metanol, que ocorre via adsorção do metanol e do acetato de etila na superfície do catalisador, seguida da formação de um intermediário tetraédrico formado pelas moléculas adsorvidas, que sofre um rearranjo formando etanol, acetato de metila, acetona e metano. Simultaneamente, parte do metanol adsorvido como metoxi monodentado é desidrogenado formando formiatos que são dessorvidos na forma de formaldeído e decompostos formando CO2 e H2

Análise dos problemas direto e inverso em um modelo de evolução populacional através de transformações integrais e inferência bayesiana

Modelos de evolução populacional são há muito tempo assunto de grande relevância, principalmente quando a população de estudo é composta por vetores de doenças. Tal importância se deve ao fato de existirem milhares de doenças que são propagadas por espécies específicas e conhecer como tais populações se comportam é vital quando pretende-se criar políticas públicas para controlar a sua proliferação. Este trabalho descreve um problema de evolução populacional difusivo com armadilhas locais e tempo de reprodução atrasado, o problema direto descreve a densidade de uma população uma vez conhecidos os parâmetros do modelo onde sua solução é obtida por meio da técnica de transformada integral generalizada, uma técnica numérico-analítica. Porém a solução do problema direto, por si só, não permite a simulação computacional de uma população em uma aplicação prática, uma vez que os parâmetros do modelo variam de população para população e precisam, portanto, ter seus valores conhecidos. Com o objetivo de possibilitar esta caracterização, o presente trabalho propõe a formulação e solução do problema inverso, estimando os parâmetros do modelo a partir de dados da população utilizando para tal tarefa dois métodos Bayesianos.

小波分析和人工神经网络在生态学研究中的应用

墨西哥帽子小波和Morlet小波在生态格局分析中的应用 本研究采用Monte Carlo方法，探讨了对小波分析的格局进行统计显著性检验的普遍方法。为了更好利用小波分析和了解两个常用小波--墨西哥帽子小波和Morlet小波在格局分析中的优缺点，用生态学研究中常见的4个模拟格局和东灵山辽东栎林的样带数据对这两个常用小波的特性进行了分析和比较。研究结果表明：墨西哥帽子小波能较好地分析样带中的斑块和间隙以及它们的位置信息，Morlet小波能较好地分析样带中尺度及其位置信息。不同的小波通常在尺度分析和斑块和间隙分析之间有平衡，所以最好的方法是结合两种小波的优点。小波分析在处理生态数据时，受所使用小波本身特性的制约。用墨西哥帽子小波进行格局分析时，小波能量谱的等值图上不同格局所对应的峰有可能相互重叠，当所分析的多尺度格局的规模差别不大时，所分析格局规模所对应的峰可能相互融合。这些小波能量谱的等值图上不同格局所对应峰的重叠和融合可能会导致格局分析量图上多个峰的相互融合和屏蔽。所以在使用小波分析做格局研究时，也应尽可能地结合小波能量谱和量图上的信息，以得到较全面和精确的格局分析信息。本研究的结论能为小波分析的应用提供指导。 应用二维小波分析对暖温带阔叶林辽东栎更新格局的研究 本研究介绍了一种二维网格空间数据分析方法一二维小波分析。该方法不仅能分析格局的等级结构，而且也能得到所分析结构的位置信息。小波系数等值图上不同格局规模的斑块和间隙可直接和不同尺度上的生态过程和生境条件相联系。小波方差从二维小波分析导出，小波方差可将四维的小波系数降至二维的小波方差函数，并量化所分析格局规模对整个格局的贡献。本研究用三个模拟格局分析了二维小波的特性及二维墨西哥帽子小波和Halo小波的特性。因为自身的特性，Halo小波比墨西哥帽子小波能提供更高的分辨率。本研究也将二维小波分析应用于暖温带阔叶林的辽东栎更新格局研究中，分析的结果表明：辽东栎的更新发生在辽东栎成树斑块和林窗斑块重叠区域。 用交互验证和独立验证来测试神人工经网络模拟水稻分檗动态的泛化能力 人工神经网络不是基于对所模拟过程的理解，而是依赖于对所分析数据的内部结构。所以人工神经网络通常被认为是经验模型而不能外推，而且在训练数据和验证数据的范围之外肯定不能精确地预测所模拟的过程。本研究通过对交互验证和独立验证神经网络模型性能的比较，测试了神经网络模型在预测水稻分檗动态方面的泛化能力。同时，也对几种提高神经网络泛化能力的技术进行了比较。研究结果表明：在训练数据的变量范围内，神经网络在预测水稻分檗动态方面具有泛化能力。较少的训练数据样本导致了对训练数据过度吻合的和不具泛化能力的神经网络。要能使神经网络在预测水稻分檗动态方面具有泛化能力，训练数据的样本量至少9倍于神经网络的权值数目。当神经网络有多个输入变量且训练数据不足以保证神经网络的泛化能力时，建议在训练之前，采用主成分分析、对应分析及类似技术压缩输入变量的个数。在压缩输入变量的个数之后，如果训练数据的样本量还不足以保证神经网络的泛化能力，就应采用提高神经网络泛化能力的技木，如：jittering和强制训练停止等，特别是神经网络与机理模型的复合模型。因为神经网络的泛化能力问题具有普遍性，所以我们的研究结论不只是适用于水稻分檗动态的预测，也适用于其它的农业和生态神经网络模型。

Coarse-level object recognition using interlevel products of complex wavelets

This paper introduces the Interlevel Product (ILP) which is a transform based upon the Dual-Tree Complex Wavelet. Coefficients of the ILP have complex values whose magnitudes indicate the amplitude of multilevel features, and whose phases indicate the nature of these features (e.g. ridges vs. edges). In particular, the phases of ILP coefficients are approximately invariant to small shifts in the original images. We accordingly introduce this transform as a solution to coarse scale template matching, where alignment concerns between decimation of a target and decimation of a larger search image can be mitigated, and computational efficiency can be maintained. Furthermore, template matching with ILP coefficients can provide several intuitive "near-matches" that may be of interest in image retrieval applications. © 2005 IEEE.

Species identification of family Lutjanidae and separation of populations of John’s snapper (Lutjanus johnii) in Persian Gulf and Oman Sea based on otolith shape analysis

The anatomical and morphometric (shape indices, contour descriptors and otolith weight) characterizations of sagittal otoliths were investigated in 13 species of Lutjanus spp. inhabiting the Persian Gulf. This is the first study that compares the efficiency of three different image analysis techniques for discriminating species based on the shape of the outer otolith contour, including elliptical Fourier descriptors (EFD), fast Fourier transform (FFT) and wavelet transform (WT). Sagittal otoliths of snappers are morphologically similar with some small specific variations. The use of otolith contour based on wavelets (WT) provided the best results in comparison with the two other methods based on Fourier descriptors, but only the combination of the all three methods (EFD, FFT and WT) was useful to obtain a robust classification of species. The species prediction improved when otolith weight was included. In relation to the shape indices, only the aspect ratio provided a clear grouping of species. Also, another study was carried on to test the possibility of application of shape analysis and comparing otolith contour of otoliths of Lutjanus johnii from Persian Gulf and Oman Sea to identify potential stocks. The results showed the otoliths have differences in contour shape and can be contribute to two different stocks.

Efficient registration of nonrigid 3-D bodies

We present a novel method to perform an accurate registration of 3-D nonrigid bodies by using phase-shift properties of the dual-tree complex wavelet transform (DT-CWT). Since the phases of DT-\BBCWT coefficients change approximately linearly with the amount of feature displacement in the spatial domain, motion can be estimated using the phase information from these coefficients. The motion estimation is performed iteratively: first by using coarser level complex coefficients to determine large motion components and then by employing finer level coefficients to refine the motion field. We use a parametric affine model to describe the motion, where the affine parameters are found locally by substituting into an optical flow model and by solving the resulting overdetermined set of equations. From the estimated affine parameters, the motion field between the sensed and the reference data sets can be generated, and the sensed data set then can be shifted and interpolated spatially to align with the reference data set. © 2011 IEEE.

Restoration of images and 3D data to higher resolution by deconvolution with sparsity regularization

Image convolution is conventionally approximated by the LTI discrete model. It is well recognized that the higher the sampling rate, the better is the approximation. However sometimes images or 3D data are only available at a lower sampling rate due to physical constraints of the imaging system. In this paper, we model the under-sampled observation as the result of combining convolution and subsampling. Because the wavelet coefficients of piecewise smooth images tend to be sparse and well modelled by tree-like structures, we propose the L0 reweighted-L2 minimization (L0RL2 ) algorithm to solve this problem. This promotes model-based sparsity by minimizing the reweighted L2 norm, which approximates the L0 norm, and by enforcing a tree model over the weights. We test the algorithm on 3 examples: a simple ring, the cameraman image and a 3D microscope dataset; and show that good results can be obtained. © 2010 IEEE.

Deconvolution and elastography based on dimensional ultrasound

This paper is in two parts and addresses two of getting more information out of the RF signal from three-dimensional (3D) mechanically-swept medical ultrasound . The first topic is the use of non-blind deconvolution improve the clarity of the data, particularly in the direction to the individual B-scans. The second topic is imaging. We present a robust and efficient approach to estimation and display of axial strain information. deconvolution, we calculate an estimate of the point-spread at each depth in the image using Field II. This is used as of an Expectation Maximisation (EM) framework in which ultrasound scatterer field is modelled as the product of (a) a smooth function and (b) a fine-grain varying function. the E step, a Wiener filter is used to estimate the scatterer based on an assumed piecewise smooth component. In the M , wavelet de-noising is used to estimate the piecewise smooth from the scatterer field. strain imaging, we use a quasi-static approach with efficient based algorithms. Our contributions lie in robust and 3D displacement tracking, point-wise quality-weighted , and a stable display that shows not only strain but an indication of the quality of the data at each point in the . This enables clinicians to see where the strain estimate is and where it is mostly noise. deconvolution, we present in-vivo images and simulations quantitative performance measures. With the blurred 3D taken as OdB, we get an improvement in signal to noise ratio 4.6dB with a Wiener filter alone, 4.36dB with the ForWaRD and S.18dB with our EM algorithm. For strain imaging show images based on 2D and 3D data and describe how full D analysis can be performed in about 20 seconds on a typical . We will also present initial results of our clinical study to explore the applications of our system in our local hospital. © 2008 IEEE.

Spread transform watermarking for video sources

Spread Transform (ST) is a quantization watermarking algorithm in which vectors of the wavelet coefficients of a host work are quantized, using one of two dithered quantizers, to embed hidden information bits; Loo had some success in applying such a scheme to still images. We extend ST to the video watermarking problem. Visibility considerations require that each spreading vector refer to corresponding pixels in each of several frames, that is, a multi-frame embedding approach. Use of the hierarchical complex wavelet transform (CWT) for a visual mask reduces computation and improves robustness to jitter and valumetric scaling. We present a method of recovering temporal synchronization at the detector, and give initial results demonstrating the robustness and capacity of the scheme.

Digital watermarking with complex wavelets

In this paper, we propose a watermarking algorithm in the complex wavelet domain. We then model watermarking as a communication process and show that the complex wavelet domain has relatively high capacity and is a potentially good domain for watermarking. Finally, a technique for registering geometrically distorted images, which is based on motion estimation in the wavelet domain, is described. The registration process can assist watermark detection in a watermarked image attacked by Stirmark, for example.

Complex wavelets and shift invariance

Recently we have developed a new form of discrete wavelet transform, which generates complex coefficients by using a dual tree of wavelet filters to obtain their real and imaginary parts. This introduces limited redundancy (2 m:1 for m-dimensional signals) and allows the transform to provide approximate shift invariance and directionally selective filters (properties lacking in the traditional wavelet transform) while preserving the usual properties of perfect reconstruction and computational efficiency with good well-balanced frequency responses. In this paper we analyse why the new transform can be designed to be shift invariant, and describe how to estimate the accuracy of this approximation and design suitable filters to achieve this.

Biologically-inspired object recognition system with features from complex wavelets

In this paper, a novel cortex-inspired feed-forward hierarchical object recognition system based on complex wavelets is proposed and tested. Complex wavelets contain three key properties for object representation: shift invariance, which enables the extraction of stable local features; good directional selectivity, which simplifies the determination of image orientations; and limited redundancy, which allows for efficient signal analysis using the multi-resolution decomposition offered by complex wavelets. In this paper, we propose a complete cortex-inspired object recognition system based on complex wavelets. We find that the implementation of the HMAX model for object recognition in [1, 2] is rather over-complete and includes too much redundant information and processing. We have optimized the structure of the model to make it more efficient. Specifically, we have used the Caltech 5 standard dataset to compare with Serre's model in [2] (which employs Gabor filter bands). Results demonstrate that the complex wavelet model achieves a speed improvement of about 4 times over the Serre model and gives comparable recognition performance. © 2011 IEEE.

Monitoring offshore pipelines using forced transverse vibration: Data analysis

Vibration methods are used to identify faults, such as spanning and loss of cover, in long off-shore pipelines. A pipeline `pig', propelled by fluid flow, generates transverse vibration in the pipeline and the measured vibration amplitude reflects the nature of the support condition. Large quantities of vibration data are collected and analyzed by Fourier and wavelet methods.

Robust pairwise matching of interest points with complex wavelets

We present a matching framework to find robust correspondences between image features by considering the spatial information between them. To achieve this, we define spatial constraints on the relative orientation and change in scale between pairs of features. A pairwise similarity score, which measures the similarity of features based on these spatial constraints, is considered. The pairwise similarity scores for all pairs of candidate correspondences are then accumulated in a 2-D similarity space. Robust correspondences can be found by searching for clusters in the similarity space, since actual correspondences are expected to form clusters that satisfy similar spatial constraints in this space. As it is difficult to achieve reliable and consistent estimates of scale and orientation, an additional contribution is that these parameters do not need to be determined at the interest point detection stage, which differs from conventional methods. Polar matching of dual-tree complex wavelet transform features is used, since it fits naturally into the framework with the defined spatial constraints. Our tests show that the proposed framework is capable of producing robust correspondences with higher correspondence ratios and reasonable computational efficiency, compared to other well-known algorithms. © 1992-2012 IEEE.

Multiply conditioned analyses of stratification in highly swirling methane/air flames

The effects of stratification on a series of highly swirling turbulent flames under globally lean conditions (φg=0.75) are investigated using a new high-spatial resolution multi-scalar dataset. This dataset features two key properties: high spatial resolution which approaches the 60 micron optical limit of the measurement system, and a wavelet oversampling methodology which significantly reduces the influence of noise. Furthermore, the very large number of realizations (30,000) acquired in the stratified cases permits statistically significant results to be obtained even after aggressive conditioning is applied. Data are doubly conditioned on equivalence ratio and the degree of stratification across the flame in each instantaneous realization. The influence of stoichiometry is limited by conditioning on the equivalence ratio at the location of peak CO mass fraction, which is shown to be a good surrogate for the location of peak heat release rate, while the stratification is quantified using a linear gradient in equivalence ratio across the instantaneous flame front. This advanced conditioning enables robust comparisons with the baseline lean premixed flame. Species mass fractions of both carbon monoxide and hydrogen are increased in temperature space under stratified conditions. Stratification is also shown to significantly increase thermal gradients, yet the derived three-dimensional flame surface density is shown to be relatively insensitive to stratification. Whilst the presence of instantaneous stratification broadens the curvature distribution relative to the premixed case, the degree of broadening is not significantly influenced by the range of global stratification ratios examined in this study. © 2012 The Combustion Institute.