Desenvolvimento e avaliação de novas abordagens de modelagem de processos de separação em leito móvel simulado

O Leito Móvel Simulado (LMS) é um processo de separação de compostos por adsorção muito eficiente, por trabalhar em um regime contínuo e também possuir fluxo contracorrente da fase sólida. Dentre as diversas aplicações, este processo tem se destacado na resolução de petroquímicos e principalmente na atualidade na separação de misturas racêmicas que são separações de um grau elevado de dificuldade. Neste trabalho foram propostas duas novas abordagens na modelagem do LMS, a abordagem Stepwise e a abordagem Front Velocity. Na modelagem Stepwise as colunas cromatográficas do LMS foram modeladas com uma abordagem discreta, onde cada uma delas teve seu domínio dividido em N células de mistura interligadas em série, e as concentrações dos compostos nas fases líquida e sólida foram simuladas usando duas cinéticas de transferência de massa distintas. Essa abordagem pressupõe que as interações decorrentes da transferência de massa entre as moléculas do composto nas suas fases líquida e sólida ocorram somente na superfície, de forma que com essa suposição pode-se admitir que o volume ocupado por cada molécula nas fases sólida e líquida é o mesmo, o que implica que o fator de residência pode ser considerado igual a constante de equilíbrio. Para descrever a transferência de massa que ocorre no processo cromatográfico a abordagem Front Velocity estabelece que a convecção é a fase dominante no transporte de soluto ao longo da coluna cromatográfica. O Front Velocity é um modelo discreto (etapas) em que a vazão determina o avanço da fase líquida ao longo da coluna. As etapas são: avanço da fase líquida e posterior transporte de massa entre as fases líquida e sólida, este último no mesmo intervalo de tempo. Desta forma, o fluxo volumétrico experimental é utilizado para a discretização dos volumes de controle que se deslocam ao longo da coluna porosa com a mesma velocidade da fase líquida. A transferência de massa foi representada por dois mecanismos cinéticos distintos, sem (tipo linear) e com capacidade máxima de adsorção (tipo Langmuir). Ambas as abordagens propostas foram estudadas e avaliadas mediante a comparação com dados experimentais de separação em LMS do anestésico cetamina e, posteriormente, com o fármaco Verapamil. Também foram comparados com as simulações do modelo de equilíbrio dispersivo para o caso da Cetamina, usado por Santos (2004), e para o caso do Verapamil (Perna 2013). Na etapa de caracterização da coluna cromatográfica as novas abordagens foram associadas à ferramenta inversa R2W de forma a determinar os parâmetros globais de transferência de massa apenas usando os tempos experimentais de residência de cada enantiômero na coluna de cromatografia líquida de alta eficiência (CLAE). Na segunda etapa os modelos cinéticos desenvolvidos nas abordagens foram aplicados nas colunas do LMS com os valores determinados na caracterização da coluna cromatográfica, para a simulação do processo de separação contínua. Os resultados das simulações mostram boa concordância entre as duas abordagens propostas e os experimentos de pulso para a caracterização da coluna na separação enantiomérica da cetamina ao longo do tempo. As simulações da separação em LMS, tanto do Verapamil quando da Cetamina apresentam uma discrepância com os dados experimentais nos primeiros ciclos, entretanto após esses ciclos iniciais a correlação entre os dados experimentais e as simulações. Para o caso da separação da cetamina (Santos, 2004), a qual a concentração da alimentação era relativamente baixa, os modelos foram capazes de predizer o processo de separação com as cinéticas Linear e Langmuir. No caso da separação do Verapamil (Perna, 2013), onde a concentração da alimentação é relativamente alta, somente a cinética de Langmuir representou o processo, devido a cinética Linear não representar a saturação das colunas cromatográficas. De acordo como o estudo conduzido ambas as abordagens propostas mostraram-se ferramentas com potencial na predição do comportamento cromatográfico de uma amostra em um experimento de pulso, assim como na simulação da separação de um composto no LMS, apesar das pequenas discrepâncias apresentadas nos primeiros ciclos de trabalho do LMS. Além disso, podem ser facilmente implementadas e aplicadas na análise do processo, pois requer um baixo número de parâmetros e são constituídas de equações diferenciais ordinárias.

Modeling object identification and tracking errors on image-based safety assessment of earthmoving operations

Object identification and tracking have become critical for automated on-site construction safety assessment. The primary objective of this paper is to present the development of a testbed to analyze the impact of object identification and tracking errors caused by data collection devices and algorithms used for safety assessment. The testbed models workspaces for earthmoving operations and simulates safety-related violations, including speed limit violations, access violations to dangerous areas, and close proximity violations between heavy machinery. Three different cases were analyzed based on actual earthmoving operations conducted at a limestone quarry. Using the testbed, the impacts of device and algorithm errors were investigated for safety planning purposes.

Multi-port network modeling of stub loaded Microstrip ring antenna for dual-band operations

A square ring microstrip antenna can be modified for dual-band operations by appropriately attaching an open ended stub. The input impedance of this antenna is analyzed here using multi-port network modeling (MNM) approach. The coupled feed is included by defining additional terms in the model. A prototype antenna is fabricated and tested to validate these computations.

Entanglement purification with higher error threshold for imperfection of local operations and bell state measurements

We analyse further the entanglement purification protocol proposed by Feng et al. (Phys. Lett. A 271 (2000) 44) in the case of imperfect local operations and measurements. It is found that this protocol allows of higher error threshold. Compared with the standard entanglement purification proposed by Bennett et al. [Phys. Rev. Lett. 76 (1996) 722], it turns out that this protocol is remarkably robust against the influences of imperfect local operations and measurements.

Purification, characterization, crystallization and theoretical molecular modeling of gyroxin fraction from Crotalus durissus terrificus venom (Laurenti, 1768)

The venom of Crotalus durissus terrificus snakes presents various substances, including a serine protease with thrombin-like activity, called gyroxin, that clots plasmatic fibrinogen and promote the fibrin formation. The aim of this study was to purify and structurally characterize the gyroxin enzyme from Crotalus durissus terrificus venom. For isolation and purification, the following methods were employed: gel filtration on Sephadex G75 column and affinity chromatography on benzamidine Sepharose 6B; 12% SDS-PAGE under reducing conditions; N-terminal sequence analysis; cDNA cloning and expression through RT-PCR and crystallization tests. Theoretical molecular modeling was performed using bioinformatics tools based on comparative analysis of other serine proteases deposited in the NCBI (National Center for Biotechnology Information) database. Protein N-terminal sequencing produced a single chain with a molecular mass of similar to 30 kDa while its full-length cDNA had 714 bp which encoded a mature protein containing 238 amino acids. Crystals were obtained from the solutions 2 and 5 of the Crystal Screen Kit (R), two and one respectively, that reveal the protein constitution of the sample. For multiple sequence alignments of gyroxin-like B2.1 with six other serine proteases obtained from snake venoms (SVSPs), the preservation of cysteine residues and their main structural elements (alpha-helices, beta-barrel and loops) was indicated. The localization of the catalytic triad in His57, Asp102 and Ser198 as well as S1 and S2 specific activity sites in Thr193 and Gli215 amino acids was pointed. The area of recognition and cleavage of fibrinogen in SVSPs for modeling gyroxin B2.1 sequence was located at Arg60, Arg72, Gln75, Arg81, Arg82, Lis85, Glu86 and Lis87 residues. Theoretical modeling of gyroxin fraction generated a classical structure consisting of two alpha-helices, two beta-barrel structures, five disulfide bridges and loops in positions 37, 60, 70, 99, 148, 174 and 218. These results provided information about the functional structure of gyroxin allowing its application in the design of new drugs.

Modeling of temperature and turbidity in a natural lake and a reservoir connected by pumped-storage operations

Pumped-storage (PS) systems are used to store electric energy as potential energy for release during peak demand. We investigate the impacts of a planned 1000 MW PS scheme connecting Lago Bianco with Lago di Poschiavo (Switzerland) on temperature and particle mass concentration in both basins. The upper (turbid) basin is a reservoir receiving large amounts of fine particles from the partially glaciated watershed, while the lower basin is a much clearer natural lake. Stratification, temperature and particle concentrations in the two basins were simulated with and without PS for four different hydrological conditions and 27 years of meteorological forcing using the software CE-QUAL-W2. The simulations showed that the PS operations lead to an increase in temperature in both basins during most of the year. The increase is most pronounced (up to 4°C) in the upper hypolimnion of the natural lake toward the end of summer stratification and is partially due to frictional losses in the penstocks, pumps and turbines. The remainder of the warming is from intense coupling to the atmosphere while water resides in the shallower upper reservoir. These impacts are most pronounced during warm and dry years, when the upper reservoir is strongly heated and the effects are least concealed by floods. The exchange of water between the two basins relocates particles from the upper reservoir to the lower lake, where they accumulate during summer in the upper hypolimnion (10 to 20 mg L−1) but also to some extent decrease light availability in the trophic surface layer.

Petri net modeling of spatial and temporal constraints in track allocation problem at railway stations

The track allocation problem (TAP) at a multi-track, multi-platform mainline railway station is defined by the station track layout and service timetable, which implies combinations of spatial and temporal conflicts. Feasible solutions are available from either traditional planning or advanced intelligent searching methods and their evaluations with respect to operational requirements are essential for the operators. To facilitate thorough analysis, a timed Coloured Petri Nets (CPN) model is presented here to encapsulate the inter-relationships of the spatial and temporal constraints in the TAP.

State Dependent Attempt Rate modeling of single cell IEEE 802.11 WLANs with homogeneous nodes and Poisson packet arrivals

We study a State Dependent Attempt Rate (SDAR) approximation to model M queues (one queue per node) served by the Carrier Sense Multiple Access with Collision Avoidance (CSMA/CA) protocol as standardized in the IEEE 802.11 Distributed Coordination Function (DCF). The approximation is that, when n of the M queues are non-empty, the (transmission) attempt probability of each of the n non-empty nodes is given by the long-term (transmission) attempt probability of n saturated nodes. With the arrival of packets into the M queues according to independent Poisson processes, the SDAR approximation reduces a single cell with non-saturated nodes to a Markovian coupled queueing system. We provide a sufficient condition under which the joint queue length Markov chain is positive recurrent. For the symmetric case of equal arrival rates and finite and equal buffers, we develop an iterative method which leads to accurate predictions for important performance measures such as collision probability, throughput and mean packet delay. We replace the MAC layer with the SDAR model of contention by modifying the NS-2 source code pertaining to the MAC layer, keeping all other layers unchanged. By this model-based simulation technique at the MAC layer, we achieve speed-ups (w.r.t. MAC layer operations) up to 5.4. Through extensive model-based simulations and numerical results, we show that the SDAR model is an accurate model for the DCF MAC protocol in single cells. (C) 2012 Elsevier B.V. All rights reserved.

Analysis and modeling of heaping behavior of granular mixtures within a computational mechanics framework

This paper presents a continuum model of the flow of granular material during filling of a silo, using a viscoplastic constitutive relation based on the Drucker-Prager plasticity yield function. The performed simulations demonstrate the ability of the model to realistically represent complex features of granular flows during filling processes, such as heap formation and non-zero inclination angle of the bulk material-air interface. In addition, micro-mechanical parametrizations which account for particle size segregation are incorporated into the model. It is found that numerical predictions of segregation phenomena during filling of a binary granular mixture agree well with experimental results. Further numerical tests indicate the capability of the model to cope successfully with complex operations involving granular mixtures.

ARMA modeling of time series based on rational approximation of spectral density function

This study is concerned with Autoregressive Moving Average (ARMA) models of time series. ARMA models form a subclass of the class of general linear models which represents stationary time series, a phenomenon encountered most often in practice by engineers, scientists and economists. It is always desirable to employ models which use parameters parsimoniously. Parsimony will be achieved by ARMA models because it has only finite number of parameters. Even though the discussion is primarily concerned with stationary time series, later we will take up the case of homogeneous non stationary time series which can be transformed to stationary time series. Time series models, obtained with the help of the present and past data is used for forecasting future values. Physical science as well as social science take benefits of forecasting models. The role of forecasting cuts across all fields of management-—finance, marketing, production, business economics, as also in signal process, communication engineering, chemical processes, electronics etc. This high applicability of time series is the motivation to this study.

Interannual and interdecadal oscillations in hydrological variables: Sources and modeling of the persistence in the Elbe River Basin

Wenn man die Existenz von physikalischen Mechanismen ignoriert, die für die Struktur hydrologischer Zeitreihen verantwortlich sind, kann das zu falschen Schlussfolgerungen bzgl. des Vorhandenseins möglicher Gedächtnis (memory) -Effekte, d.h. von Persistenz, führen. Die hier vorgelegte Doktorarbeit spürt der niedrigfrequenten klimatischen Variabilität innerhalb den hydrologischen Zyklus nach und bietet auf dieser "Reise" neue Einsichten in die Transformation der charakteristischen Eigenschaften von Zeitreihen mit einem Langzeitgedächtnis. Diese Studie vereint statistische Methoden der Zeitreihenanalyse mit empirisch-basierten Modelltechniken, um operative Modelle zu entwickeln, die in der Lage sind (1) die Dynamik des Abflusses zu modellieren, (2) sein zukünftiges Verhalten zu prognostizieren und (3) die Abflusszeitreihen an unbeobachteten Stellen abzuschätzen. Als solches präsentiert die hier vorgelegte Dissertation eine ausführliche Untersuchung zu den Ursachen der niedrigfrequenten Variabilität von hydrologischen Zeitreihen im deutschen Teil des Elbe-Einzugsgebietes, den Folgen dieser Variabilität und den physikalisch basierten Reaktionen von Oberflächen- und Grundwassermodellen auf die niedrigfrequenten Niederschlags-Eingangsganglinien. Die Doktorarbeit gliedert sich wie folgt: In Kapitel 1 wird als Hintergrundinformation das Hurst Phänomen beschrieben und ein kurzer Rückblick auf diesbezügliche Studien gegeben. Das Kapitel 2 diskutiert den Einfluss der Präsenz von niedrigfrequenten periodischen Zeitreihen auf die Zuverlässigkeit verschiedener Hurst-Parameter-Schätztechniken. Kapitel 3 korreliert die niedrigfrequente Niederschlagsvariabilität mit dem Index der Nord-Atlantischen Ozillations (NAO). Kapitel 4-6 sind auf den deutschen Teil des Elbe-Einzugsgebietes fokussiert. So werden in Kapitel 4 die niedrigfrequenten Variabilitäten der unterschiedlichen hydro-meteorologischen Parameter untersucht und es werden Modelle beschrieben, die die Dynamik dieser Niedrigfrequenzen und deren zukünftiges Verhalten simulieren. Kapitel 5 diskutiert die mögliche Anwendung der Ergebnisse für die charakteristische Skalen und die Verfahren der Analyse der zeitlichen Variabilität auf praktische Fragestellungen im Wasserbau sowie auf die zeitliche Bestimmung des Gebiets-Abflusses an unbeobachteten Stellen. Kapitel 6 verfolgt die Spur der Niedrigfrequenzzyklen im Niederschlag durch die einzelnen Komponenten des hydrologischen Zyklus, nämlich dem Direktabfluss, dem Basisabfluss, der Grundwasserströmung und dem Gebiets-Abfluss durch empirische Modellierung. Die Schlussfolgerungen werden im Kapitel 7 präsentiert. In einem Anhang werden technische Einzelheiten zu den verwendeten statistischen Methoden und die entwickelten Software-Tools beschrieben.

Characterization of glycerol kinase from baker's yeast: Response surface modeling of the enzymatic reaction

The present study describes a methodology of dosage of glycerol kinase (GK) from baker's yeast. The standardization of the activity of the glycerol kinase from baker's yeast was accomplished using the diluted enzymatic preparation containing glycerol phosphate oxidase (GPO) and glycerol kinase. The mixture was incubated at 60 degrees C by 15 min and the reaction was stopped by the SDS solution addition. A first set of experiments was carried out in order to investigate the individual effect of temperature (7), pH and substrate concentration (S), on GK activity and stability. The pH and temperature stability tests showed that the enzyme presented a high stability to pH 6.0-8.0 and the thermal stability were completely maintained up to 50 degrees C during 1 h. The K(m) of the enzyme for glycerol was calculated to be 2 mM and V(max) to be 1.15 U/mL. In addition, modeling and optimization of reaction conditions was attempted by response surface methodology (RSM). Higher activity values will be attained at temperatures between 52 and 56 degrees C, pH around 10.2-10.5 and substrate concentrations from 150 to 170 mM.This low cost method for glycerol kinase dosage in a sequence of reactions is of great importance for many industries, like food, sugar and alcohol. RSM showed to be an adequate approach for modeling the reaction and optimization of reaction conditions to maximize glycerol kinase activity. (C) 2007 Elsevier B.V. All rights reserved.

Finite element modeling of the cement-bone interface beneath the tibial tray of a total knee arthroplasty: Study of the stress shielding effect (modellazione agli elementi finiti dell'interfaccia cemento-osso sotto il piatto tibiale di protesi totale di ginocchio: Analisi dello stress shielding)

The goal of this thesis was the study of the cement-bone interface in the tibial component of a cemented total knee prosthesis. One of the things you can see in specimens after in vivo service is that resorption of bone occurs in the interdigitated region between bone and cement. A stress shielding effect was investigated as a cause to explain bone resorption. Stress shielding occurs when bone is loaded less than physiological and therefore it starts remodeling according to the new loading conditions. µCT images were used to obtain 3D models of the bone and cement structure and a Finite Element Analysis was used to simulate different kind of loads. Resorption was also simulated by performing erosion operations in the interdigitated bone region. Finally, 4 models were simulated: bone (trabecular), bone with cement, and two models of bone with cement after progressive erosions of the bone. Compression, tension and shear test were simulated for each model in displacement-control until 2% of strain. The results show how the principal strain and Von Mises stress decrease after adding the cement on the structure and after the erosion operations. These results show that a stress shielding effect does occur and rises after resorption starts.

Observations and modeling of the Marginal Ice Zone

Global climate change in recent decades has strongly influenced the Arctic generating pronounced warming accompanied by significant reduction of sea ice in seasonally ice-covered seas and a dramatic increase of open water regions exposed to wind [Stephenson et al., 2011]. By strongly scattering the wave energy, thick multiyear ice prevents swell from penetrating deeply into the Arctic pack ice. However, with the recent changes affecting Arctic sea ice, waves gain more energy from the extended fetch and can therefore penetrate further into the pack ice. Arctic sea ice also appears weaker during melt season, extending the transition zone between thick multi-year ice and the open ocean. This region is called the Marginal Ice Zone (MIZ). In the Arctic, the MIZ is mainly encountered in the marginal seas, such as the Nordic Seas, the Barents Sea, the Beaufort Sea and the Labrador Sea. Formed by numerous blocks of sea ice of various diameters (floes) the MIZ, under certain conditions, allows maritime transportation stimulating dreams of industrial and touristic exploitation of these regions and possibly allowing, in the next future, a maritime connection between the Atlantic and the Pacific. With the increasing human presence in the Arctic, waves pose security and safety issues. As marginal seas are targeted for oil and gas exploitation, understanding and predicting ocean waves and their effects on sea ice become crucial for structure design and for real time safety of operations. The juxtaposition of waves and sea ice represents a risk for personnel and equipment deployed on ice, and may complicate critical operations such as platform evacuations. The risk is difficult to evaluate because there are no long-term observations of waves in ice, swell events are difficult to predict from local conditions, ice breakup can occur on very short time-scales and wave-ice interactions are beyond the scope of current forecasting models [Liu and Mollo-Christensen, 1988,Marko, 2003]. In this thesis, a newly developed Waves in Ice Model (WIM) [Williams et al., 2013a,Williams et al., 2013b] and its related Ocean and Sea Ice model (OSIM) will be used to study the MIZ and the improvements of wave modeling in ice infested waters. The following work has been conducted in collaboration with the Nansen Environmental and Remote Sensing Center and within the SWARP project which aims to extend operational services supporting human activity in the Arctic by including forecast of waves in ice-covered seas, forecast of sea-ice in the presence of waves and remote sensing of both waves and sea ice conditions. The WIM will be included in the downstream forecasting services provided by Copernicus marine environment monitoring service.