Advanced chemometric methods: Applicability on industrial data

Recent years have produced great advances in the instrumentation technology. The amount of available data has been increasing due to the simplicity, speed and accuracy of current spectroscopic instruments. Most of these data are, however, meaningless without a proper analysis. This has been one of the reasons for the overgrowing success of multivariate handling of such data. Industrial data is commonly not designed data; in other words, there is no exact experimental design, but rather the data have been collected as a routine procedure during an industrial process. This makes certain demands on the multivariate modeling, as the selection of samples and variables can have an enormous effect. Common approaches in the modeling of industrial data are PCA (principal component analysis) and PLS (projection to latent structures or partial least squares) but there are also other methods that should be considered. The more advanced methods include multi block modeling and nonlinear modeling. In this thesis it is shown that the results of data analysis vary according to the modeling approach used, thus making the selection of the modeling approach dependent on the purpose of the model. If the model is intended to provide accurate predictions, the approach should be different than in the case where the purpose of modeling is mostly to obtain information about the variables and the process. For industrial applicability it is essential that the methods are robust and sufficiently simple to apply. In this way the methods and the results can be compared and an approach selected that is suitable for the intended purpose. Differences in data analysis methods are compared with data from different fields of industry in this thesis. In the first two papers, the multi block method is considered for data originating from the oil and fertilizer industries. The results are compared to those from PLS and priority PLS. The third paper considers applicability of multivariate models to process control for a reactive crystallization process. In the fourth paper, nonlinear modeling is examined with a data set from the oil industry. The response has a nonlinear relation to the descriptor matrix, and the results are compared between linear modeling, polynomial PLS and nonlinear modeling using nonlinear score vectors.

Strukturbildung durch Selbstorganisation von Oligonukleotiden

Die DNA-Doppelhelix ist eine relativ dicke (Ø ≈ 2 nm), kompakte und dadurch auf kurzen Längenskalen relativ steife Verbindung (lp[dsDNA] ≈ 50-60 nm), mit einer klar definierten Struktur, die durch biologische Methoden sehr präzise manipuliert werden kann. Die Auswirkungen der primären Sequenz auf die dreidimensionale Strukturbildung ist gut verstanden und exakt vorhersagbar. Des Weiteren kann DNA an verschiedenen Stellen mit anderen Molekülen verknüpft werden, ohne dass ihre Selbsterkennung gestört wird. Durch die helikale Struktur besteht außerdem ein Zusammenhang zwischen der Lage und der räumlichen Orientierung von eingeführten Modifikationen. Durch moderne Syntheseverfahren lassen sich beliebige Oligonukleotidsequenzen im Bereich bis etwa 150-200 Basen relativ preiswert im Milligrammmaßstab herstellen. Diese Eigenschaften machen die DNA zu einem idealen Kandidaten zur Erzeugung komplexer Strukturen, die durch Selbsterkennung der entsprechenden Sequenzen gebildet werden. In der hier vorgelegten Arbeit wurden einzelsträngige DNA-Abschnitte (ssDNA) als adressierbare Verknüpfungsstellen eingesetzt, um verschiedene molekulare Bausteine zu diskreten nicht periodischen Strukturen zu verbinden. Als Bausteine dienten flexible synthetische Polymerblöcke und semiflexible Doppelstrang-DNA-Abschnitte (dsDNA), die an beiden Enden mit unterschiedlichen Oligonukleotidsequenzen „funktionalisiert“ sind. Die zur Verknüpfung genutzten Oligonukleotidabschnitte wurden so gewählt (n > 20 Basen), dass ihre Hybridisierung zu einer bei Raumtemperatur stabilen Doppelstrangbildung führt. Durch Kombination der Phosphoramiditsynthese von DNA mit einer festkörpergestützten Blockkopplungsreaktion konnte am Beispiel von Polyethylenoxiden ein sehr effektiver Syntheseweg zur Herstellung von ssDNA1-PEO-ssDNA2-Triblockcopolymeren entwickelt werden, der sich problemlos auf andere Polymere übertragen lassen sollte. Die Längen und Basenabfolgen der beiden Oligonukleotidsequenzen können dabei unabhängig voneinander frei gewählt werden. Somit wurden die Voraussetzungen geschaffen, um die Selbsterkennung von Oligonukleotiden durch Kombination verschiedener Triblockcopolymere zur Erzeugung von Multiblockcopolymeren zu nutzen, die mit klassischen Synthesetechniken nicht zugänglich sind. Semiflexible Strukturelemente lassen sich durch die Synthese von Doppelstrangfragmenten mit langen überstehenden Enden (sticky-ends) realisieren. Die klassischen Ansätze der molekularen Genetik zur Erzeugung von sticky-ends sind in diesem Fall nicht praktikabel, da sie zu Einschränkungen im Bezug auf Länge und Sequenz der überhängenden Enden führen. Als Methode der Wahl haben sich zwei verschiedene Varianten der Polymerase Kettenreaktion (PCR) erwiesen, die auf der Verwendung von teilkomplementären Primern beruhen. Die eigentlichen Primersequenzen wurden am 5´-Ende entweder über ein 2´-Desoxyuridin oder über einen kurzen Polyethylenoxid-Spacer (n = 6) mit einer frei wählbaren „sticky-end-Sequenz“ verknüpft. Mit diesen Methoden sind sowohl 3´- als auch 5´-Überhänge zugänglich und die Länge der Doppelstrangabschnitte kann über einen breiten Molmassenbereich sehr exakt eingestellt werden. Durch Kombination derartiger Doppelstrangfragmente mit den biosynthetischen Triblockcopolymeren lassen sich Strukturen erzeugen, die als Modellsysteme zur Untersuchung verschiedener Biomoleküle genutzt werden können, die in Form eines mehrfach gebrochenen Stäbchens vorliegen. Im letzten Abschnitt wurde gezeigt, dass durch geeignete Wahl der überstehenden Enden bzw. durch Hybridisierung der Doppelstrangfragmente mit passenden Oligonukleotiden verzweigte DNA-Strukturen mit Armlängen von einigen hundert Nanometern zugänglich sind. Im Vergleich zu den bisher veröffentlichten Methoden bietet diese Herangehensweise zwei entscheidende Vorteile: Zum einen konnte der Syntheseaufwand auf ein Minimum reduziert werden, zum anderen ist es auf diesem Weg möglich die Längen der einzelnen Arme, unabhängig voneinander, über einen breiten Molmassenbereich zu variieren.

Simulação numérica do escoamento monofásico em uma bomba centrífuga radial

Centrifugal pumps are vastly used in many industrial applications. Knowledge of how these components behave in several circumstances is crucial for the development of more efficient and, therefore, less expensive pumping installations. The combination of multiple impellers, vaned diffusers and a volute might introduce several complex flow characteristics that largely deviate from regular inviscid pump flow theory. Computational Fluid Dynamics can be very helpful to extract information about which physical phenomena are involved in such flows. In this sense, this work performs a numerical study of the flow in a two-stage centrifugal pump (Imbil ITAP 65-330/2) with a vaned diffuser and a volute. The flow in the pump is modeled using the software Ansys CFX, by means of a multi-block, transient rotor-stator technique, with structured grids for all pump parts. The simulations were performed using water and a mixture of water and glycerin as work fluids. Several viscosities were considered, in a range between 87 and 720 cP. Comparisons between experimental data obtained by Amaral (2007) and numerical head curves showed a good agreement, with an average deviation of 6.8% for water. The behavior of velocity, pressure and turbulence kinetic energy fields was evaluated for several operational conditions. In general, the results obtained by this work achieved the proposed goals and are a significant contribution to the understanding of the flow studied.

Factores de rentabilização do processo de serragem de granitos com engenhos multi-lâminas

Este trabalho visa apresentar um enquadramento da realidade económica e industrial do sector transformador de granitos ornamentais em Portugal e fazer uma análise do processo de serragem, com engenhos multi-lâminas e granalha de aço, na medida em que este é o método de seccionamento de blocos de granito mais utilizado pelas grandes indústrias do sector. Tendo em conta a importância económica desta operação produtiva na indústria em causa, foi definido como fito deste projecto a análise estatística dos custos de produção; a definição de fórmulas de cálculo que permitam prever o custo médio de serragem; e o estudo de soluções economicamente viáveis e ambientalmente sustentáveis para o problema das lamas resultantes do expurgo dos engenhos. Para a persecução deste projecto foi realizada uma recolha de dados implementando rotinas de controlo e registo dos mesmos, em quadros de produção normalizados e de fácil preenchimento, pelos operadores destes equipamentos. Esta recolha de dados permitiu isolar, quantificar e formular os factores de rentabilização do processo de serragem selecionando, dentro da amostra de estudo obtida, um conjunto de serragens com características similares e com valores próximos dos valores da média estatística. Apartir dos dados destas serragens foram geradas curvas de tendência polinomial com as quais se analisaram as variações provocadas no custo médio de serragem, pelas variações do factor em estudo. A formulação dos factores de rentabilização e os dados estatísticos obtidos permitiram depois o desenvolvimento de fórmulas de cálculo do custo médio de serragem que establecem o custo de produção diferenciado em função das espessuras com, ou sem, a incorporação dos factores de rentabilização. Como consequência do projecto realizado obteve-se um conjunto de conclusões util, para o sector industrial em causa, que evidencia a importancia da Ocupação dos engenhos e rentabilização de um espaço confinado, da Resistência oferecida à serragem pelos granitos, e da Diferença de altura entre os blocos de uma mesma carga, nos custos de transformação.

Modeling for control design of a multi-reach water canal

This article addresses the problem of obtaining reduced complexity models of multi-reach water delivery canals that are suitable for robust and linear parameter varying (LPV) control design. In the first stage, by applying a method known from the literature, a finite dimensional rational transfer function of a priori defined order is obtained for each canal reach by linearizing the Saint-Venant equations. Then, by using block diagrams algebra, these different models are combined with linearized gate models in order to obtain the overall canal model. In what concerns the control design objectives, this approach has the advantages of providing a model with prescribed order and to quantify the high frequency uncertainty due to model approximation. A case study with a 3-reach canal is presented, and the resulting model is compared with experimental data. © 2014 IEEE.

Modeling for control design of a multi-reach water canal

This article addresses the problem of obtaining reduced complexity models of multi-reach water delivery canals that are suitable for robust and linear parameter varying (LPV) control design. In the first stage, by applying a method known from the literature, a finite dimensional rational transfer function of a priori defined order is obtained for each canal reach by linearizing the Saint-Venant equations. Then, by using block diagrams algebra, these different models are combined with linearized gate models in order to obtain the overall canal model. In what concerns the control design objectives, this approach has the advantages of providing a model with prescribed order and to quantify the high frequency uncertainty due to model approximation. A case study with a 3-reach canal is presented, and the resulting model is compared with experimental data. © 2014 IEEE.

Positioning Janus nanoparticles in block copolymer scaffolds

The periodic domains formed by block copolymer melts have been heralded as potential scaffolds for arranging nanoparticles in 3d space, provided we can control the positioning of the particles. Recent experiments have located particles at the domain interfaces by grafting mixed brushes to their surfaces. Here the underlying mechanism, which involves the transformation into Janus particles, is investigated with self-consistent field theory using a new multi-coordinate-system algorithm.

Bundle Block Adjustment of CBERS-2B HRC Imagery Combining Control Points and Lines

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Decentralized AC power flow for real-time multi-TSO power system operation

This paper adjusts decentralized OPF optimization to the AC power flow problem in power systems with interconnected areas operated by diferent transmission system operators (TSO). The proposed methodology allows finding the operation point of a particular area without explicit knowledge of network data of the other interconnected areas, being only necessary to exchange border information related to the tie-lines between areas. The methodology is based on the decomposition of the first-order optimality conditions of the AC power flow, which is formulated as a nonlinear programming problem. To allow better visualization of the concept of independent operation of each TSO, an artificial neural network have been used for computing border information of the interconnected TSOs. A multi-area Power Flow tool can be seen as a basic building block able to address a large number of problems under a multi-TSO competitive market philosophy. The IEEE RTS-96 power system is used in order to show the operation and effectiveness of the decentralized AC Power Flow. ©2010 IEEE.

Exterior orientation of CBERS-2B imagery using multi-feature control and orbital data

The major contribution of this paper relates to the practical advantages of combining Ground Control Points (GCPs), Ground Control Lines (GCLs) and orbital data to estimate the exterior orientation parameters of images collected by CBERS-2B (China-Brazil Earth Resources Satellite) HRC (High-resolution Camera) and CCD (High-resolution CCD Camera) sensors. Although the CBERS-2B is no longer operational, its images are still being used in Brazil, and the next generations of the CBERS satellite will have sensors with similar technical features, which motivates the study presented in this paper. The mathematical models that relate the object and image spaces are based on collinearity (for points) and coplanarity (for lines) conditions. These models were created in an in-house developed software package called TMS (Triangulation with Multiple Sensors) with multi-feature control (GCPs and GCLs). Experiments on a block of four CBERS-2B HRC images and on one CBERS-2B CCD image were performed using both models. It was observed that the combination of GCPs and GCLs provided better bundle block adjustment results than conventional bundle adjustment using only GCPs. The results also demonstrate the advantages of using primarily orbital data when the number of control entities is reduced. © 2013 International Society for Photogrammetry and Remote Sensing, Inc. (ISPRS).

Genetic gain in the selection by multi-effects index in open-pollinated progenies of Eucalyptus grandis Hill ex Maiden

In Brazil, Eucalyptus grandis Hill ex Maiden is widely used for commercial reforestation, especially for production of pulp, paper and energy. Its genetic variability is being explored in tree improvement programs for over 30 years. The objective of this work was to estimate genetic parameters and compare genetic gains by multi-effects index in a breeding population of E. grandis. Progeny tests were established using open-pollinated seeds from ten provenances ranging from 153 to 160 progenies established in a completely randomized block design in four sites of Sao Paulo State (Anhembi, Avere Itarare e Pratania). At 24 months of age the traits diameter at breast height (DBH), height (ALT) and volume (VOL) were measured. The individual site analyses indicated significant genetic differences among progenies, height genetic variability and the mean progeny heritability (> 0.70). For joint analyses of sites, significant differences in genotype x environmental interaction effects were detected, showing differences of performance of the progenies in different sites. The Itarare site gave high genetic gains, effective size and genetic diversity. The genetic diversity and low effective size are unviable factors; considering that the progeny tests studied should retain adequate levels of genetic variability in order to be transformed in future seedling seed orchards.

Locating control points in aerial images with a multi-scale approach based on terrestrial image patches

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Multi-target-directed ligands: application to the Alzheimer's disease

The MTDL (multi-target-directed ligand) design strategy is used to develop single chemical entities that are able to simultaneously modulate multiple targets. The development of such compounds might disclose new avenues for the treatment of a variety of pathologies (e.g. cancer, AIDS, neurodegenerative diseases), for which an effective cure is urgently needed. This strategy has been successfully applied to Alzheimer’s disease (AD) due to its multifactorial nature, involving cholinergic dysfunction, amyloid aggregation, and oxidative stress. Despite many biological entities have been recognized as possible AD-relevant, only four achetylcholinesterase inhibitors (AChEIs) and one NMDA receptor antagonist are used in therapy. Unfortunately, such compounds are not disease-modifying agents behaving only as cognition enhancers. Therefore, MTDL strategy is emerging as a powerful drug design paradigm: pharmacophores of different drugs are combined in the same structure to afford hybrid molecules. In principle, each pharmacophore of these new drugs should retain the ability to interact with its specific site(s) on the target and, consequently, to produce specific pharmacological responses that, taken together, should slow or block the neurodegenerative process. To this end, the design and synthesis of several examples of MTDLs for combating neurodegenerative diseases have been published. This seems to be the more appropriate approach for addressing the complexity of AD and may provide new drugs for tackling the multifactorial nature of AD, and hopefully stopping its progression. According to this emerging strategy, in this work thesis different classes of new molecular structures, based on the MTDL approach, have been developed. Moreover, curcumin and its constrained analogs have currently received remarkable interest as they have a unique conjugated structure which shows a pleiotropic profile that we considered a suitable framework in developing MTDLs. In fact, beside the well-known direct antioxidant activity, curcumin displays a wide range of biological properties including anti-inflammatory and anti-amyloidogenic activities and an indirect antioxidant action through activation of the cytoprotective enzyme heme oxygenase (HO-1). Thus, since many lines of evidence suggest that oxidative stess and mitochondria impairment have a cental role in age-related neurodegenerative diseases such as AD, we designed mitochondria-targeted antioxidants by connecting curcumin analogs to different polyamine chains that, with the aid of electrostatic force, might drive the selected antioxidant moiety into mitochondria.

Kinematics of the Sicily and Calabria Subduction System from Elastic Block Modeling of GPS Data

We use data from about 700 GPS stations in the EuroMediterranen region to investigate the present-day behavior of the the Calabrian subduction zone within the Mediterranean-scale plates kinematics and to perform local scale studies about the strain accumulation on active structures. We focus attenction on the Messina Straits and Crati Valley faults where GPS data show extentional velocity gradients of ∼3 mm/yr and ∼2 mm/yr, respectively. We use dislocation model and a non-linear constrained optimization algorithm to invert for fault geometric parameters and slip-rates and evaluate the associated uncertainties adopting a bootstrap approach. Our analysis suggest the presence of two partially locked normal faults. To investigate the impact of elastic strain contributes from other nearby active faults onto the observed velocity gradient we use a block modeling approach. Our models show that the inferred slip-rates on the two analyzed structures are strongly impacted by the assumed locking width of the Calabrian subduction thrust. In order to frame the observed local deformation features within the present- day central Mediterranean kinematics we realyze a statistical analysis testing the indipendent motion (w.r.t. the African and Eurasias plates) of the Adriatic, Cal- abrian and Sicilian blocks. Our preferred model confirms a microplate like behaviour for all the investigated blocks. Within these kinematic boundary conditions we fur- ther investigate the Calabrian Slab interface geometry using a combined approach of block modeling and χ2ν statistic. Almost no information is obtained using only the horizontal GPS velocities that prove to be a not sufficient dataset for a multi-parametric inversion approach. Trying to stronger constrain the slab geometry we estimate the predicted vertical velocities performing suites of forward models of elastic dislocations varying the fault locking depth. Comparison with the observed field suggest a maximum resolved locking depth of 25 km.