Uso da calibração multivariada para a predição de propriedades físico-químicas de misturas de óleo de soja e biodiesel

O objetivo deste trabalho foi estabelecer um modelo empregando-se ferramentas de regressão multivariada para a previsão do teor em ésteres metílicos e, simultaneamente, de propriedades físico-químicas de misturas de óleo de soja e biodiesel de soja. O modelo foi proposto a partir da correlação das propriedades de interesse com os espectros de reflectância total atenuada no infravermelho médio das misturas. Para a determinação dos teores de ésteres metílicos foi utilizada a cromatografia líquida de alta eficiência (HPLC), podendo esta ser uma técnica alternativa aos método de referência que utilizam a cromatografia em fase gasosa (EN 14103 e EN 14105). As propriedades físico-químicas selecionadas foram índice de refração, massa específica e viscosidade. Para o estudo, foram preparadas 11 misturas com diferentes proporções de biodiesel de soja e de óleo de soja (0-100 % em massa de biodiesel de soja), em quintuplicata, totalizando 55 amostras. A região do infravermelho estudada foi a faixa de 3801 a 650 cm-1. Os espectros foram submetidos aos pré-tratamentos de correção de sinal multiplicativo (MSC) e, em seguida, à centralização na média (MC). As propriedades de interesse foram submetidas ao autoescalamento. Em seguida foi aplicada análise de componentes principais (PCA) com a finalidade de reduzir a dimensionalidade dos dados e detectar a presença de valores anômalos. Quando estes foram detectados, a amostra era descartada. Os dados originais foram submetidos ao algoritmo de Kennard-Stone dividindo-os em um conjunto de calibração, para a construção do modelo, e um conjunto de validação, para verificar a sua confiabilidade. Os resultados mostraram que o modelo proposto por PLS2 (Mínimos Quadrados Parciais) foi capaz de se ajustar bem os dados de índice de refração e de massa específica, podendo ser observado um comportamento aleatório dos erros, indicando a presença de homocedasticidade nos valores residuais, em outras palavras, o modelo construído apresentou uma capacidade de previsão para as propriedades de massa específica e índice de refração com 95% de confiança. A exatidão do modelo foi também avaliada através da estimativa dos parâmetros de regressão que são a inclinação e o intercepto pela Região Conjunta da Elipse de Confiança (EJCR). Os resultados confirmaram que o modelo MIR-PLS desenvolvido foi capaz de prever, simultaneamente, as propriedades índice de refração e massa específica. Para os teores de éteres metílicos determinados por HPLC, foi também desenvolvido um modelo MIR-PLS para correlacionar estes valores com os espectros de MIR, porém a qualidade do ajuste não foi tão boa. Apesar disso, foi possível mostrar que os dados podem ser modelados e correlacionados com os espectros de infravermelho utilizando calibração multivariada

Filtragem adaptativa aplicada à redução de desvios em séries temporais de previsão numérica climática.

Esta dissertação apresenta resultados da aplicação de filtros adaptativos, utilizando os algoritmos NLMS (Normalized Least Mean Square) e RLS (Recursive Least Square), para a redução de desvios em previsões climáticas. As discrepâncias existentes entre o estado real da atmosfera e o previsto por um modelo numérico tendem a aumentar ao longo do período de integração. O modelo atmosférico Eta é utilizado operacionalmente para previsão numérica no CPTEC/INPE e como outros modelos atmosféricos, apresenta imprecisão nas previsões climáticas. Existem pesquisas que visam introduzir melhorias no modelo atmosférico Eta e outras que avaliam as previsões e identificam os erros do modelo para que seus produtos sejam utilizados de forma adequada. Dessa forma, neste trabalho pretende-se filtrar os dados provenientes do modelo Eta e ajustá-los, de modo a minimizar os erros entre os resultados fornecidos pelo modelo Eta e as reanálises do NCEP. Assim, empregamos técnicas de processamento digital de sinais e imagens com o intuito de reduzir os erros das previsões climáticas do modelo Eta. Os filtros adaptativos nesta dissertação ajustarão as séries ao longo do tempo de previsão. Para treinar os filtros foram utilizadas técnicas de agrupamento de regiões, como por exemplo o algoritmo de clusterização k-means, de modo a selecionar séries climáticas que apresentem comportamentos semelhantes entre si. As variáveis climáticas estudadas são o vento meridional e a altura geopotencial na região coberta pelo modelo de previsão atmosférica Eta com resolução de 40 km, a um nível de pressão de 250 hPa. Por fim, os resultados obtidos mostram que o filtro com 4 coeficientes, adaptado pelo algoritmo RLS em conjunto com o critério de seleção de regiões por meio do algoritmo k-means apresenta o melhor desempenho ao reduzir o erro médio e a dispersão do erro, tanto para a variável vento meridional quanto para a variável altura geopotencial.

Topic 1. Some steric-height features of the water off the Pacific coast of Canada; Topic 2. Possible warming of the water at station P in the northeast Pacific during 1956-1984 [abstract]

TOPIC 1: In terms of seasonal scale, temperature effect dominates the annual change of steric height in the open ocean whereas salinity effect controls it along the continental shelf. Large portion of the annual change of height relative to the 1000-db surface is contained in the upper 100m layer. However, in interannual scale large anomalies of steric height in the open ocean, are more often than not, caused by halosteric rather than thermosteric effect. At least in the open ocean the heights are almost totally determined by the behavior of deep water. Their interannual variability appears to be related to the cumulative effect of Eckman pumping. TOPIC 2: There is a "trend" that over the past 28 years the water at Station P has warmed. Least-square analysis indicates that this warming may be significant but shortening of the time-series data by approximately 10 years fails to show that this is the case. These "trends" have to be interpreted with care. The warming may be "apparent" in that it is not indicated clearly in the deep isopynal surfaces which, during the above period, have deepened. Thus warming at the isobaric surfaces may be the effect of the downward migration of the isopynal surfaces.

Age and growth of the swordfish (Xiphias gladius L.) in the waters around Taiwan determined from anal-fin rays

Age and growth of the swordfish (Xiphias gladius) in Taiwan waters was studied from counts of growth bands on cross sections of the second ray of the first anal fin. Data on lower jaw fork length and weight, and samples of the anal fin of male and female swordfish were collected from three offshore and coastal tuna longline fishing ports on a monthly basis between September 1997 and March 1999. In total, 685 anal fins were collected and 627 of them (293 males and 334 females) were aged successfully. The lower jaw fork lengths of the aged individuals ranged from 83.4 to 246.6 cm for the females and from 83.3 to 206 cm for the males. The radii of the fin rays and growth bands on the cross sections were measured under a dissecting microscope equipped with an image analysis system. Trends in the monthly marginal increment ratio indicated that growth bands formed once a year. Thus, the age of each fish was deter-mined from the number of visible growth bands. Two methods were used to estimate and compare the standard and the generalized von Bertalanffy growth parameters for both males and females. The nonlinear least square estimates of the generalized von Bertalanffy growth parameters in method II, in which a power function was used to describe the relationship between ray radius and LJFL, were recommended as most acceptable. There were significant differences in growth parameters between males and females. The growth parameters estimated for females were the following: asymptotic length (L∞) = 300.66 cm, growth coefficient (K) = 0.040/yr, age at zero length (t0) = –0.75 yr, and the fitted fourth parameter (m) = –0.785. The growth parameters estimated for males were the following: asymptotic length (L∞) = 213.05 cm, growth coefficient (K) = 0.086/yr, age at zero length (t0) = –0.626 yr, and the fitted fourth parameter (m) = –0.768.

中药青蒿萜类代谢物谱分析及青蒿素生物合成的研究

青蒿素是从中药青蒿，学名黄花蒿（Artemisia annua L.）植物地上部分分离出的抗疟疾有效单体，为一种倍半萜内酯类化合物，其生物合成途径属于植物类异戊二烯代谢途径。青蒿素生物合成途径及其调控机制仍不完全清楚，本论文采用GC-MS 和GC×GC-TOFMS 方法对青蒿萜类代谢物谱进行检测，用多维统计学方法对检测结果进行整理和比较分析，研究青蒿素生物合成及其与青蒿中其他萜类代谢的关系，取得了以下结果： 一、通过GC×GC-TOFMS 方法对青蒿挥发油成分进行分析，共鉴定出303 种组分。其中挥发油中相对百分含量大于1%的10 种组分中有9 种为萜类化合物，含量接近总挥发油的50%。在相对百分含量大于0.1%的49 种成分中，有30 种萜类化合物。有27 种相对百分含量大于0.1%的成分首次在青蒿挥发油中报道，其中包括10 种萜类化合物。 二、利用GC-MS 方法分析了青蒿001 和SP18 两个青蒿素高产株系不同生长时期萜类代谢物谱，结果表明：青蒿中萜类化合物在不同时期合成和积累是动态变化的，萜类化合物的种类和数量在营养生长期随生长时间的延长而提高，在营养生长后期和现蕾前期达到最高水平，进入生殖生长后随生长时间的延长而迅速降低。通过多维统计PLS-DA（Partial Leasted Square Discriminant Analysis） 分析，确定001 中有17 个化合物的含量在不同生长时期有明显变化，其中15 个为萜类化合物。SP18 中有18 个化合物的含量在不同生长时期有明显变化，其中16 个为萜类化合物。青蒿素，青蒿酸，二氢青蒿酸，青蒿素B 都是含量变化明显的标记物。其中青蒿酸和二氢青蒿酸含量在营养生长后期达到最高水平，进入生殖生长后迅速下降，而青蒿素和青蒿素B 在整个检测时期含量变化相对较小，在营养生长时期含量已经较高，在现蕾前期含量稍有上升，进入现蕾期后有所下降，本研究确定现蕾前期为代谢物谱分析最佳取样时期，并为药材采收提供指导。 三、不同基因型青蒿代谢物谱研究表明，青蒿素高产株系SP18 和001 代谢物表现出一定的差异，通过多维统计PLS-DA 分析，共找出了22 种在两种基因型中差异明显的化合物，其中包括倍半萜化合物12 种，单萜化合物3 种，三萜化合物4 种。SP18 特征化合物为樟脑和两个未鉴定倍半萜化合物，而001 特征化合物是龙脑和β-法呢烯。另外两种基因型中青蒿素及相关前体化合物的积累模式差异明显，SP18 中二氢青蒿酸和青蒿素含量高，而青蒿酸和青蒿素B 含量极低；001 中二氢青蒿酸和青蒿素含量相对SP18 要低，但青蒿素B 和青蒿酸含量比SP18 要高。该结果表明在青蒿素高产株系中，青蒿素含量与二氢青蒿酸的含量呈正相关，结合Brown 等的活体标记研究结果分析，从二氢青蒿酸到青蒿素的转化可能是青蒿素合成的限速步骤。 四、利用GC×GC-TOFMS 方法对转基因青蒿萜类代谢物谱进行了分析，共对200 个左右化合物峰进行PLS-DA 和OSC-PLS (Orthogonal Signal Correction–Partial leasted Square)多维统计分析，结果表明：青蒿萜类代谢物谱在外源基因转入后发生显著变化，与对照株系相比均呈现显著差异。其中过量表达Amorpha-4,11-diene 合酶基因（ads）株系中青蒿素及相关化合物变化最明显，而过量表达FPP 合酶基因（fps）株系中青蒿素及相关化合物变化相对较小，在受到调控而成为差异标记物的化合物中，70%是倍半萜类化合物。 五、考察了外源茉莉酸甲酯对青蒿素生物合成的影响，结果表明：300 μM 外源茉莉酸甲酯能提高青蒿素含量，在处理后第8 天青蒿素含量提高38%。青蒿萜类代谢物谱研究表明，茉莉酸甲酯不仅可以诱导青蒿中青蒿素的合成，还能诱导很多化合物，特别是倍半萜和三萜类的合成。OSC-PLS 分析结果找出了9 个处理后含量明显提高的标记物，其中6 个倍半萜化合物，3 个三萜化合物。标记物鲨烯含量提高了67%，另一个未鉴定出结构的倍半萜提高了60%，这些化合物可能与青蒿素有着类似的调控机制，而外源喷洒茉莉酸甲酯可以作为提高青蒿素产量的有效途径之一。

Real time feature-based facial tracking using Lie algebras

We have developed a novel human facial tracking system that operates in real time at a video frame rate without needing any special hardware. The approach is based on the use of Lie algebra, and uses three-dimensional feature points on the targeted human face. It is assumed that the roughly estimated facial model (relative coordinates of the three-dimensional feature points) is known. First, the initial feature positions of the face are determined using a model fitting technique. Then, the tracking is operated by the following sequence: (1) capture the new video frame and render feature points to the image plane; (2) search for new positions of the feature points on the image plane; (3) get the Euclidean matrix from the moving vector and the three-dimensional information for the points; and (4) rotate and translate the feature points by using the Euclidean matrix, and render the new points on the image plane. The key algorithm of this tracker is to estimate the Euclidean matrix by using a least square technique based on Lie algebra. The resulting tracker performed very well on the task of tracking a human face.

Long-term changes and variability of monthly extreme temperatures in India

Extreme temperatures are changing worldwide together with changes in the mean temperatures. This study investigates the long-term trends and variations of the monthly maximum and minimum temperatures and their effects on seasonal fluctuations in various climatological regions in India. The magnitude of the trends and their statistical significance were determined by parametric ordinary least square regression techniques and the variations were determined by the respective coefficient of variations. The results showed that the monthly maximum temperature increased, though unevenly, over the last century. Minimum temperature changes were more variable than maximum temperature changes, both temporally and spatially, with results of lesser significance. The results of this study are good indicators of Indian climate variability and its changes over the last century. © Springer-Verlag 2009.

Assessing seasonal precipitation trends in India using parametric and non-parametric statistical techniques

This paper provides an insight into the long-term trends of the four seasonal and annual precipitations in various climatological regions and sub-regions in India. The trends were useful to investigate whether Indian seasonal rainfall is changing in terms of magnitude or location-wise. Trends were assessed over the period of 1954-2003 using parametric ordinary least square fits and non-parametric Mann-Kendall technique. The trend significance was tested at the 95% confidence level. Apart from the trends for individual climatological regions in India and the average for the whole of India, trends were also specifically determined for the possible smaller geographical areas in order to understand how different the trends would be from the bigger spatial scales. The smaller geographical regions consist of the whole southwestern continental state of Kerala. It was shown that there are decreasing trends in the spring and monsoon rainfall and increasing trends in the autumn and winter rainfalls. These changes are not always homogeneous over various regions, even in the very short scales implying a careful regional analysis would be necessary for drawing conclusions regarding agro-ecological or other local projects requiring change in rainfall information. Furthermore, the differences between the trend magnitudes and directions from the two different methods are significantly small and fall well within the significance limit for all the cases investigated in Indian regions (except where noted). © 2010 Springer-Verlag.

Biology and distribution of grouper (Epinephelus coioides) in province waters (Abadan Bhrakan)

This survay has been done from Januray 2000 till May 2002 in Khouzestan costal waters. Four species of grouper were identified from which orange spotted grouper (Epinephelus coioides) was the dominant species. For studing environmental parameters and reproductive biology, age, growth parameters and mortality rate samples were collected by fishing ship. Samples were taken montly in 4 days by fishing traps and trawls. In addition, some samples were obtained from Khozestan fish landing centres. Environmental factors such as PH, 02, salinity, water temperature and depth of traping areas, were measured. To identify species, morphometric characteries of 452 individal fishes were measured. Stomach contents of 394 fish were has survaid, from which stomach of 226 fish, and 168 fish had empty stomachs. Percentage of empty stomachs (cv) in males was more than females. Food items found in 73 percent of stomach were crab (11%), shrimps (8.8%) , squids (3.9%), gastropods (17%) and bivalves (0.4%). Feeding intensity in year classes did not obay logic trends The importance relatively indicator (I.R.I) were 81, 9.9, 4, 1.5 and 0.3 percent for fish, crab, shrimp, squid, gastropod and bivalve respectively. For age determination, sagita otoliths of 450 fish were taken and countable sections were obtained from 425 specimens. Relative frequency distribution of opaque and transparent rings showed that each opaque growth ring generates once a year from November to September. It seemed that generation of opaque rings is affected by temperature and photoperiod changes. Correlation between length and age was calculated using Von Bertalanffy's least square method. Following equasion was obtaind: L(t) : 122.27 (1 e 0.146 (t+0.482)) Growth parameters were determined through by Ford Walford equasion and Response Surface and Shepherd subcommands in Elefan program and L00 and K amounts were have determined. Correlation between length and age of 635 fish was determined by gender . Length and age correlation was calculated by exponential model and between total length and standard length by straghit line model. Correlation between age and weight of sagita was calculated by total length and age. The most Correlation was between sagita weight and fish age (r=0.876). Total mortality rate (z) was estimated by Length Converthed Method , Jones and Vanzaling and Powel Wetherall. Total mortality rate was z=0.39. Natural mortality rate, using Pauly method was calculated M=0.32. Fishing mortality (F) was 0.08. Gonads of 425 fishes were surveid within 18 month, from which 363 were female, 46 were male and 16 were sex reversing individuals .Total length of females varied from 26 to 95.5 centimeters while males length varied from 56.5 to 107 centimeters. Sex reversing individuals had a length of 47.5 centimeters, when two years old and 62.5 centimeters at age of 3 years. From the mentioned 425 fish, 401 individuals were matured, containing 339 females and 62 males, 5.47 females against each male. Montly changes of Gonadosomatic Index (GSI) by total body weight and standard length and total body length showed that this index increases from march to May and maximum increase was in May . This experiment was adapted in spawning season. Potential, relative, and absoulate fecundity was estimated by counting eggs in three samples. Total amount of traped fish using special traps was 16182.18 kg from which Epinephelus coioides provided catching 15353.43 kg of it (91.27 %) and By catch was 141.18 kg (8.24 %). Total average CPUE for whole catch was 123.33 kg/day/vessel. Total amount of catch was estimated 232.04 tons, considering CPUE of total catch and total Khuzestan trap ships effort.

Fast L0-based sparse signal recovery

This paper develops an algorithm for finding sparse signals from limited observations of a linear system. We assume an adaptive Gaussian model for sparse signals. This model results in a least square problem with an iteratively reweighted L2 penalty that approximates the L0-norm. We propose a fast algorithm to solve the problem within a continuation framework. In our examples, we show that the correct sparsity map and sparsity level are gradually learnt during the iterations even when the number of observations is reduced, or when observation noise is present. In addition, with the help of sophisticated interscale signal models, the algorithm is able to recover signals to a better accuracy and with reduced number of observations than typical L1-norm and reweighted L1 norm methods. ©2010 IEEE.

Mixed source model and its adapted vocal tract filter estimate for voice transformation and synthesis

In current methods for voice transformation and speech synthesis, the vocal tract filter is usually assumed to be excited by a flat amplitude spectrum. In this article, we present a method using a mixed source model defined as a mixture of the Liljencrants-Fant (LF) model and Gaussian noise. Using the LF model, the base approach used in this presented work is therefore close to a vocoder using exogenous input like ARX-based methods or the Glottal Spectral Separation (GSS) method. Such approaches are therefore dedicated to voice processing promising an improved naturalness compared to generic signal models. To estimate the Vocal Tract Filter (VTF), using spectral division like in GSS, we show that a glottal source model can be used with any envelope estimation method conversely to ARX approach where a least square AR solution is used. We therefore derive a VTF estimate which takes into account the amplitude spectra of both deterministic and random components of the glottal source. The proposed mixed source model is controlled by a small set of intuitive and independent parameters. The relevance of this voice production model is evaluated, through listening tests, in the context of resynthesis, HMM-based speech synthesis, breathiness modification and pitch transposition. © 2012 Elsevier B.V. All rights reserved.

Engine modelling for diesel smoke feedback control system design

A novel smoke sensor was used to measure the smoke response to the fuel rack on a diesel engine. The conventional modelling methods used for engine control were investigated. The synchronization technique and Recursive Least Square method were applied to engine modelling and two models for controller design were derived.

Quantitative structure-property relationships for octanol-air partition coefficients of polychlorinated naphthalenes, chlorobenzenes and p,p '-DDT

The octanol-air partition coefficient (K-OA) is a key descriptor of chemicals partitioning between the atmosphere and environmental organic phases. Quantitative structure-property relationships (QSPR) are necessary to model and predict KOA from molecular structures. Based on 12 quantum chemical descriptors computed by the PM3 Hamiltonian, using partial least squares (PLS) analysis, a QSPR model for logarithms of K-OA to base 10 (log K-OA) for polychlorinated naphthalenes (PCNs), chlorobenzenes and p,p'-DDT was obtained. The cross-validated Q(cum)(2) value of the model is 0.973, indicating a good predictive ability of the model. The main factors governing log K-OA of the PCNs, chlorobenzenes, and p,p'-DDT are, in order of decreasing importance, molecular size and molecular ability of donating/accepting electrons to participate in intermolecular interactions. The intermolecular dispersive interactions play a leading role in governing log K-OA. The more chlorines in PCN and chlorobenzene molecules, the greater the log K-OA values. Increasing E-LUMO (the energy of the lowest unoccupied molecular orbital) of the molecules leads to decreasing log K-OA values, implying possible intermolecular interactions between the molecules under study and octanol molecules. (C) 2002 Elsevier Science Ltd. All rights reserved.

Quantitative relationships between molecular structures, environmental temperatures and octanol-air partition coefficients of PCDD/Fs

A concise quantitative model that incorporates information on both environmental temperature M and molecular structures, for logarithm of octanol-air partition coefficient (K-OA) to base 10 (logK(OA)) of PCDDs, was developed. Partial least squares (PLS) analysis together with 14 quantum chemical descriptors were used to develop the quantitative relationships between structures, environmental temperatures and properties (QRSETP) model. It has been validated that the obtained QRSETP model can be used to predict logK(OA) of other PCDDs. Molecular size, environmental temperature (T), q(+) (the most positive net atomic charge on hydrogen or chlorine atoms in PCDD molecules) and E-LUMO (the energy of the lowest unoccupied molecular orbital) are main factors governing logK(OA) of PCDD/Fs under study. The intermolecular dispersive interactions and thus the size of the molecules play a leading role in governing logK(OA). The more chlorines in PCDD molecules, the greater the logK(OA) values. Increasing E-LUMO values of the molecules leads to decreasing logK(OA) values, implying possible intermolecular interactions between the molecules under study and octanol molecules. Greater q(+) values results in greater intermolecular electrostatic repulsive interactions between PCDD and octanol molecules and smaller logK(OA) values. (C) 2002 Elsevier Science B.V. All rights reserved.

Quantitative structure-property relationships for octanol-air partition coefficients of polychlorinated biphenyls

Based on nine quantum chemical descriptors computed by PM3 Hamiltonian, using partial least squares analysis, a significant quantitative structure-property relationship for the logarithm of octanol-air partition coefficients (log K-OA) of polychlorinated biphenyls (PCBs) was obtained. The cross-validated Q(cum)(2) value of the model is 0.962, indicating a good predictive ability. The intermolecular dispersive interactions and thus the size of the PCB molecules play a key role in governing log K-OA. The greater the size of PCB molecules, the greater the log K-OA values. Increasing E-LUMO (the energy of the lowest unoccupied molecular orbital) values of the PCBs leads to decreasing log K-OA values, indicating possible interactions between PCB and octanol molecules. Increasing Q(Cl)(+) (the most positive net atomic charges on a chlorine atom) and Q(C)(-) (the largest negative net atomic charge on a carbon atom) values of PCBs results in decreasing log K-OA values, implying possible intermolecular electrostatic interactions between octanol and PCB molecules. (C) 2002 Elsevier Science Ltd. All rights reserved.