Es werden die Strukturbildung und Benetzung zweidimensionaler (2D) Phasen von Langmuir-Monolagen im lokalen thermodynamischen Gleichgewicht untersucht. Eine Langmuir-Monolage ist ein isoliertes 2D System von Surfaktanten an der Wasser/Luft-Grenzfläche, in dem kristalline, flüssigkristalline, flüssige oder gasförmige Phasen auftreten, die sich in Positionsordnung und/oder Orientierungsordnung unterscheiden. Permanente elektrische Dipolmomente der Surfaktanten führen zu einer langreichweitigen repulsiven Selbstwechselwirkung der Monolage und zur Bildung mesoskopischer Strukturen. Es wird ein Wechselwirkungsmodell verwendet, das die Strukturbildung als Wechselspiel kurzreichweitiger Anziehung (nackte Linienspannung) und langreichweitiger Abstoßung (Oberflächenpotential) auf einer Skala Delta beschreibt. Physikalisch trennt Delta die beiden Längenskalen der lang- und kurzreichweitigen Wechselwirkung. In dieser Arbeit werden die thermodynamischen Stabilitätsbedingungen für die Form einer Phasengrenzlinie (Young-Laplace-Gleichung) und Dreiphasenkontaktpunkt (Young-Bedingung) hergeleitet und zur Beschreibung experimenteller Daten genutzt: Die Linienspannung benetzender 2D Tropfen wird mit Hilfe hängender-Tropfen-Tensiometrie gemessen. Die Blasenform und -größe von 2D Schäumen wird theoretisch modelliert und mit experimentellen 2D Schäumen verglichen. Kontaktwinkel werden durch die Anpassung von experimentellen Tropfen mit numerischen Lösungen der Young-Laplace-Gleichung auf Mikrometerskalen gemessen. Das Skalenverhalten des Kontaktwinkels ermöglicht die Bestimmung einer unteren Schranke von Delta. Weiterhin wird diskutiert, inwieweit das Schalten von 2D Benetzungsmodi in biologischen Membranen zur Steuerung der Reaktionskinetik ein Rolle spielen könnte. Hierzu werden Experimente aus unserer Gruppe, die in einer Langmuir-Monolage durchgeführt wurden, herangezogen. <br /> <br /> Abschließend wird die scheinbare Verletzung der Gibbs&prime;schen Phasenregel in Langmuir-Monolagen (nicht-horizontales Plateau der Oberflächendruck-Fläche Isotherme, ausgedehntes Dreiphasengebiet in Einkomponentensystemen) quantitativ untersucht. Eine Verschmutzung der verwendeten Substanzen ist demnach die wahscheinlichste Erklärung, während Finite-Size-Effekte oder der Einfluss der langreichweitigen Elektrostatik die Größenordnung des Effektes nicht beschreiben können. / The present work investigates the structure formation and wetting in two dimensional (2D) Langmuir monolayer phases in local thermodynamic equilibrium. A Langmuir monolayer is an isolated 2D system of surfactants at the air/water interface. It exhibits crystalline, liquid crystalline, liquid and gaseous phases differing in positional and/or orientational order. Permanent electric dipole moments of the surfactants lead to a long range repulsive interaction and to the formation of mesoscopic patterns. An interaction model is used describing the structure formation as a competition between short range attraction (bare line tension) and long range repulsion (surface potentials) on a scale Delta. Delta has the meaning of a dividing length between the short and long range interaction. In the present work the thermodynamic equilibrium conditions for the shape of two phase boundary lines (Young-Laplace equation) and three phase intersection points (Young&prime;s condition) are derived and applied to describe experimental data: The line tension is measured by pendant droplet tensiometry. The bubble shape and size of 2D foams is calculated numerically and compared to experimental foams. Contact angles are measured by fitting numerical solutions of the Young-Laplace equation on micron scale. The scaling behaviour of the contact angle allows to measure a lower limit for Delta. Further it is discussed, whether in biological membranes wetting transitions are a way in order to control reaction kinetics. Studies performed in our group are discussed with respect to this question in the framework of the above mentioned theory.<br /> <br /> Finally the apparent violation of Gibbs&prime; phase rule in Langmuir monolayers (non-horizontal plateau of the surface pressure/area-isotherm, extended three phase coexistence region in one component systems) is investigated quantitatively. It has been found that the most probable explanation are impurities within the system whereas finite size effects or the influence of the long range electrostatics can not explain the order of magnitude of the effect.

Persistent organic pollutants (POPs) are toxic chemicals that can be found in various matrices in all corners of the planet, including remote areas such as the Arctic.  Several POPs are known and monitored but given the abundance of new chemicals in commerce about which little is known, chemicals that may be new POPs are constantly being screened for. The use of flame retardants, particularly brominated flame retardants (BFRs), has been increasing for decades. PBDEs and HBCDDs are two types of BFRs that have historically been used in large volumes but recently faced legislative restrictions. However, in order to meet fire safety standards, these BFRs have been replaced by a variety of emerging flame retardants (EFRs) about which little is known especially concerning their toxicity, production volumes, and environmental behavior. The main purpose of this thesis was to investigate the occurrence and fate in indoor and outdoor environments of several EFRs and compare them with PBDEs, HBCDDs, and legacy POPs. Several indoor environments in the city of Stockholm, Sweden were sampled for dust, indoor air, and ventilation system air (Paper II).  Results from these samples revealed a number of EFRs that humans are exposed to and that are emitted from buildings through ventilation systems. These included DDC-CO, DBE-DBCH, PBT, HBB, EHTBB, and BEH-TEBP. PBDE levels seem to be declining compared to previous studies in Stockholm.  Outdoor air and soil were sampled across transects of Stockholm (Paper II) and Birmingham, United Kingdom (Paper III).  Results from these samples showed the presence of many of the same EFRs in the outdoor environment that were found in indoor environments.  Urban pulses in air were discovered for PBDEs in both cities and for some EFRs in Stockholm, indicating that the cities are sources of EFRs to the outdoor environment.  Atmospheric deposition samples were taken at two sites in northern Sweden (Paper I).  Three EFRs (DDC-CO, DBE-DBCH, and BTBPE) and two current-use pesticides (trifluralin and chlorothalonil) were identified, indicating these compounds’ potential for long range transport and global contamination.  Other legacy POPs such as HCH, PCBs, and PBDEs were measured in the deposition samples as well.  The bulk of deposition was comprised of HCH and PCBs with only minor contributions from PBDEs, chlordanes, and emerging compounds.  Finally, passive and active air sampling methods were compared for BFRs in offices in Beijing, China.  Some EFRs were identified in indoor air from China; however, BDE-209 was the most predominant compound found (Paper IV).  Air samples collected with passive samplers generally had measured FR concentrations within a factor of 2-3 of those collected with active samplers. The use of a GFF in the passive samplers resulted in concentrations of particle-bound contaminants such as BDE-209 that were more comparable to those in active samples. The positioning of the PUF in the passive samplers affected the sampling rates for gaseous compounds and particle retention on PUFs was shown to be a large source of uncertainty in passive sampling. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Manuscript.</p><p> </p>

Doctor of Philosophy (PhD) / This thesis mainly builds on the Variance Gamma (VG) model for financial assets over time of Madan & Seneta (1990) and Madan, Carr & Chang (1998), although the model based on the t distribution championed in Heyde & Leonenko (2005) is also given attention. The primary contribution of the thesis is the development of VG models, and the extension of t models, which accommodate a dependence structure in asset price returns. In particular it has become increasingly clear that while returns (log price increments) of historical financial asset time series appear as a reasonable approximation of independent and identically distributed data, squared and absolute returns do not. In fact squared and absolute returns show evidence of being long range dependent through time, with autocorrelation functions that are still significant after 50 to 100 lags. Given this evidence against the assumption of independent returns, it is important that models for financial assets be able to accommodate a dependence structure.

Doctor of Philosophy (PhD) / This thesis mainly builds on the Variance Gamma (VG) model for financial assets over time of Madan & Seneta (1990) and Madan, Carr & Chang (1998), although the model based on the t distribution championed in Heyde & Leonenko (2005) is also given attention. The primary contribution of the thesis is the development of VG models, and the extension of t models, which accommodate a dependence structure in asset price returns. In particular it has become increasingly clear that while returns (log price increments) of historical financial asset time series appear as a reasonable approximation of independent and identically distributed data, squared and absolute returns do not. In fact squared and absolute returns show evidence of being long range dependent through time, with autocorrelation functions that are still significant after 50 to 100 lags. Given this evidence against the assumption of independent returns, it is important that models for financial assets be able to accommodate a dependence structure.

Diss. Linköping : Linköpings universitet, 2005.

Τα τελευταία χρόνια, η ραγδαία αύξηση των χρηστών ασύρματης επικοινωνίας και η ολοένα και αυξανόμενη ζήτηση πιο αποδοτικών επικοινωνιών μεταξύ των χρηστών, έστρεψαν το ενδιαφέρον της επιστημονικής κοινότητας στην μελέτη πιο ευέλικτων ασύρματων δικτύων. Ιδιαίτερο ενδιαφέρον προς αυτή την κατεύθυνση παρουσιάζουν τα Γνωστικά Συστήματα Ραδιοεπικοινωνιών (Cognitive Radios). Τα Γνωστικά Συστήματα είναι ευφυή συστήματα τα οποία έχουν την ικανότητα να αντιλαμβάνονται τα χαρακτηριστικά του περιβάλλοντος στο οποίο βρίσκονται και να προσαρμόζουν κατάλληλα τις παραμέτρους της μετάδοσης τους με στόχο πιο αξιόπιστες και πιο ευέλικτες επικοινωνίες. Ιδιαίτερο χαρακτηριστικό αυτών των συστημάτων είναι το γεγονός ότι μπορούν να συνυπάρξουν ταυτόχρονα δύο είδη χρηστών, οι κύριοι και οι δευτερεύοντες. Κύριοι είναι οι χρήστες οι οποίοι έχουν νόμιμη άδεια χρήσης μιας ζώνης συχνοτήτων από κάποια αρμόδια αρχή, ενώ δευτερεύοντες ονομάζονται οι χρήστες του δικτύου που δεν έχουν άδεια χρήσης κάποιας ζώνης συχνοτήτων αλλά υπό κατάλληλες συνθήκες μπορούν να χρησιμοποιήσουν κάποια ζώνη που ανήκει στους κύριους χρήστες. Η μετάδοση των δευτερευόντων χρηστών γίνεται με τέτοιο τρόπο (συχνότητα και χρόνο μετάδοσης), ώστε να μην δημιουργείται παρεμβολή στους κύριους χρήστες. Πρόσφατα, το ερευνητικό ενδιαφέρον στράφηκε προς την χαρτογράφηση κάποιον φαινομένων σε τέτοιου είδους συστήματα. Πιο συγκεκριμένα, με τον όρο χαρτογράφηση εννοούμε την μελέτη ενός φαινομένου, όπως για παράδειγμα της παρεμβολής ή του κέρδους του καναλιού όχι μόνο ως προς το χρόνο αλλά και ως προς το χώρο. Για παράδειγμα, στα γνωστικά συστήματα η χαρτογράφηση του καναλιού δίνει τη δυνατότητα στους δευτερεύοντες χρήστες ανά πάσα στιγμή να γνωρίζουν το πιθανό κανάλι επικοινωνίας προς όλα τα σημεία του χώρου που μελετούμε. Κάτι τέτοιο, λόγω της ιδιαιτερότητας αυτού του συστήματος, μπορεί να δώσει πολύτιμες πληροφορίες για τον τρόπο με τον οποίο μπορούν να εκπέμψουν οι δευτερεύοντες χρήστες έτσι ώστε να μην παρεμβάλλονται στην μετάδοση των κύριων χρηστών. Οι εργασίες που σχετίζονται με τα γνωστικά συστήματα μέχρι τώρα είχαν ως στόχο την μελέτη είτε της επισκίασης είτε της παρεμβολής που μετριέται σε ένα σημείο του χώρου. Στα πλαίσια της παρούσας διπλωματικής εργασίας, στόχος μας ήταν η μελέτη της μακροπρόθεσμης πρόβλεψης (long range prediction) ενός καναλιού σε ένα δίκτυο κινούμενων γνωστικών χρηστών, κάτι το οποίο δεν έχει μελετηθεί έως τώρα. Με τον όρο μακροπρόθεσμη πρόβλεψη καναλιού αναφερόμαστε στην εκτίμηση του καναλιού σε κάποια επόμενη χρονική στιγμή. Δεδομένου ότι το κανάλι επηρεάζεται τόσο από φαινόμενα μικρής όσο και από ευρείας κλίμακας στρέψαμε το ενδιαφέρον μας σε ένα ενοποιημένο μοντέλο καναλιού που περιλαμβάνει και τα δύο είδη εξασθένησης. Αυτή η μακροπρόθεσμη πρόβλεψη του χρονικά μεταβαλλόμενου καναλιού αποσκοπεί στην χαρτογράφηση των διαθέσιμων καναλιών στο χώρο αλλά και στο χρόνο, πληροφορία που μπορεί να φανεί πολύ χρήσιμη σε διάφορες εφαρμογές όπως αυτή της δρομολόγησης πακέτων πληροφορίας σε ένα δίκτυο, ή της κατανομής ενέργειας στα γνωστικά και σε άλλα ασύρματα συστήματα. Πιο συγκεκριμένα, στο κεφάλαιο 1, θα αναφερθούμε στις νέες τάσεις που ακολουθούνται στις ασύρματες επικοινωνίες. Αρχικά θα αναφερθούμε στις συνεργατικές επικοινωνίες και τις λεγόμενες συντονισμένες μεταδόσεις πολλαπλών σημείων ενώ στην συνέχεια θα επικεντρωθούμε στα γνωστικά δίκτυα και τις λειτουργίες που επιτελούν. Στο κεφάλαιο 2 θα περιγράψουμε με λεπτομέρεια τους μηχανισμούς διάδοσης των ηλεκρομαγνητικών κυμάτων και τα δύο βασικά είδη εξασθένησης που παραμορφώνουν το λαμβανόμενο σήμα στον δέκτη. Στη συνέχεια του κεφαλαίου αυτού θα περιγράψουμε διάφορα μοντέλα που περιγράφουν τα δύο είδη εξασθένησης και τέλος, θα παρουσιάσουμε ένα μοντέλο που τα συνδυάζει. Στο κεφάλαιο 3, θα παρουσιάσουμε ένα ενοποιημένο μοντέλο το οποίο συμπεριλαμβάνει τόσο τα μικρής όσο και τα μεγάλης κλίμακας φαινόμενα το οποίο θα υιοθετήσουμε στην συνέχεια στην πειρματική μας διαδικασία. Επιπλέον, θα παρουσιάσουμε τους λόγους για τους οποίους στρέψαμε την προσοχή μας στο εν λόγω θέμα. Στο κεφάλαιο 4 θα αναφερθούμε στην έννοια της χαρτογράφησης ενός φαινομένου σε ένα γνωστικό σύστημα και στην τρέχουσα βιβλιογραφία. Πιο συγκεκριμένα, θα κάνουμε μία ιστορική αναδρομή της χρήσης της χαρτογράφησης στα γνωστικά συστήματα. Ξεκινώντας από την χαρτογράφηση της παρεμβολής σε ένα δίκτυο και την χαρτογράφηση του φάσματος, θα επικεντρωθούμε στην χαρτογράφηση των φαινομένων ευρείας κλίμακας και ειδικά στην χαρτογράφηση της επισκίασης. Στο κεφάλαιο 5 θα μελετήσουμε την έννοια της εκτίμησης και παρακολούθησης καναλιού και θα επικεντρωθούμε σε παραμετρικά κανάλια. Στο τέλος του κεφαλαίου, θα διευρύνουμε την παρακολούθηση ενός καναλιού με την διαδικασία της μακροπρόθεσμης πρόβλεψης του κέρδους του καναλιού. Αυτή η επιπλέον γνώση της μακροπρόθεσμης πρόβλεψης σε συνδυασμό με διαδικασίες χωρικής παρεμβολής σε ένα γνωστικό σύστημα μπορεί να βελτιώσει πολύ τις συνθήκες μετάδοσης. Λόγω της ιδιαιτερότητας που παρουσιάζουν τα εν λόγω συστήματα κάθε επιπλέον μακροπρόθεσμη πληροφορία της κατάστασης του δικτύου μπορεί να βοηθήσει σε σημαντικές αποφάσεις κατανομής ισχύος ή μετάδοσης ώστε να ελαχιστοποιηθεί η παρεμβολή προς τους κύριους χρήστες. Στο κεφάλαιο 6 θα περιγράψουμε με λεπτομέρεια το πρόβλημα μακροπρόθεσμης πρόβλεψης με το οποίο ασχοληθήκαμε και θα παρουσιάσουμε μία σειρά από πειραματικά αποτελέσματα που σχετίζονται με την ποιότητα της πρόβλεψης του καναλιού κάτω από διαφορετικές συνθήκες. Τέλος, στο κεφάλαιο 7 θα αναφερθούμε στα συμπεράσματα που προέκυψαν από την συγκεκριμένη διπλωματική εργασία καθώς και σε κάποιες μελλοντικές κατευθύνσεις που παρουσιάζουν ιδιαίτερο ενδιαφέρον. Οι κατευθύνσεις αυτές σχετίζονται τόσο για το συγκεκριμένο αλγόριθμο που χρησιμοποιήσαμε όσο και με πιθανές εφαρμογές του. / In recent years, the use of wireless communication systems has rapidly increased along with the demand for more resource hungry applications. To support such demands, the research community has been focusing into new more efficient and more flexible communications techniques and systems. To this end, the so-called cognitive radio systems are of particular interest. In a cognitive system, the participating communication nodes are able of understanding the special characteristics of the surrounding environment and adjust, accordingly, their transmission parameters in order to achieve a reliable level of communication. An identifying element of such systems is the co-existence of two kinds of users, i.e. the primary and the secondary ones. The first are licensed users of a specific transmission band as opposed to the second, who are not licensed to use such a band, however under certain constraints and conditions they are allowed to. Their transmission is performed in an appropriate manner so as not to interfere with the primary users. Currently, there is an active research interest in the so-called cartography of certain phenomena that occur in the wireless medium used by systems like the cognitive ones. Specifically, the term cartography is used for the study of a phenomenon such as the gain of channel through time and space for any pair of points in a given region. This information could, for example, support the decision making procedure of a secondary user related to the selection of a transmission band to use for transmission, reducing in this way the produced interference level. The research efforts, so far, has been focusing on the cartography of either the shadowing phenomenon or the interference that is present at a particular point at space. In this master thesis, the main target is the study of long-range channel prediction algorithms in a cognitive network of mobile users that take into account both small and large scale fading. The phrase “long-range channel prediction” refers to the process of predict the value of the channel at a future time instant. In order to capture the twofold nature to fading, i.e. small and large scale one, a unifying channel model is adopted. This operation and the predicted information aim at providing the necessary tools in order to map the available channels into space as well as time. This information can be valuable in numerous applications such as routing of data packets and resource allocation. In more detail, chapter 1 is an introduction to wireless communications focusing on their history and the new directions that look to the future. Specifically, a description will be provided for the evolution of cellular and ad hoc wireless networks along with three new tendencies, i.e. cooperative communications, coordinated multipoint or transmissions and cognitive networks. In chapter 2, an introduction of the wireless medium for transmitting communications signals is presented. Specifically, at first, the propagation mechanisms of electromagnetic waves along with their two main sources of fading that distort signals will be provided. Then, appropriate models for the fading sources will be described which are useful for developing and evaluating communications algorithms. A unified model that incorporates both small and large-scale fading is presented in chapter 3. This model will be used later in this thesis during the experimental analysis. Moreover, a motivation of looking into this direction will be provided. In chapter 4, a bibliographic presentation of cartography will be presented. The chapter will start with a historical review of chartography. First, the focus will be on the mapping of interference and spectrum usage. Then, the focus will shift towards the mapping of large scale phenonena, especially, the mapping of shadowing. The estimation/tracking and prediction of wireless channels will be the main focus of chapter 5. Parametric channels and associated algorithms will be presented. Moreover, a long rage prediction algorithm, that is studied in this thesis, will be described in detail. This additional information combined with spatial interpolation techniques can, in general, be used to improve the transmission conditions in a cognitive system. This information, in such systems, can assist in decision making procedures related to power allocations and transmissions, so as to mitigate the interference among the users. The aforementioned synthesized channel model along with the long rage prediction problem that is studied in this thesis will be evaluated in chapter 6. In this chapter, exhaustive simulations have been conducted targeting the prediction performance under different propagation conditions. Finally, in chapter 7, the main conclusions drawn in this thesis along with some future research directions will be provided. The directions are related both with the specific algorithm that was studied and some possible applications.

Os príons são proteínas que causam um grupo de doenças neurodegenerativas invariavelmente fatais, sendo uma das mais conhecidas a encefalopatia espongiforme bovina (ou doença da vaca louca). A proteína príon celular (PrPc), rica em estrutura α-helicoidal, sofre uma mudança na sua estrutura secundária produzindo a proteína patológica (PrPSc; o príon) na qual prevalecem folhas-β. Devido a falta de dados de estruturais de alta resolução dos príons, simulações de DM podem ser particularmente úteis para estudar o redobramento de PrP. Estudos experimentais e computacionais, descritos na literatura, indicam que a utilização de pH ácido é capaz de criar alguma instabilidade estrutural, produzindo um ganho de estrutura-β na região N-terminal antes desestruturada. Este trabalho se propõe a investigar computacionalmente as mudanças estruturais na proteína príon celular do hamster Sírio induzidas por alteração de pH. Para isso, foi avaliada a influência do uso de diferentes campos de força (GROMOS, AMBER e OPLS), diferentes estados de protonação dos resíduos de histidina, diferentes condições iniciais e diferentes métodos de cálculo de interações eletrostáticas de longo alcance (GRF e SPME). A partir da evolução temporal das estruturas secundárias, foi observada uma forte dependência dos resultados com o uso de diferentes parâmetros de simulação. De fato, a tendência de pH descrita na literatura não foi claramente observada neste trabalho. Isso pode estar associado com a necessidade de se investir mais em múltiplas simulações de dinâmica molecular para quantificar com maior precisão o comportamento estrutural dos fragmentos protéicos em cada pH de estudo. / Prions are proteins that cause a group of invariably fatal neurodegenerative diseases, one of the most known being bovine spongiform encephalopathy (or mad cow disease). The cellular prion protein (PrPc), rich in α-helical structure, undergoes a change in its secondary structure producing the pathological protein (PrPSc, the prion) in which β-sheet structure prevails. Because of the lack of high-resolution prion structural data, MD simulations can be particularly useful to study PrP misfolding. Experimental and computational studies, described in literature, indicate that the use of low pH is capable to create some structural instability, producing a gain of β-structure content in the otherwise unstructured N-terminal region. This work aims to investigate computationally structural changes in the cellular prion protein of Syrian hamster induced by pH change. For this, we evaluated the influence of different force fields (GROMOS, AMBER and OPLS), different protonation states of histidine residues, different initial conditions and different methods for calculating long-range electrostatic interactions (GRF and SPME). From the time evolution of the secondary structures, we observed a strong dependence on the simulation parameters. In fact, the pH tendency described in literature was not clearly observed in this work. It may be associated with the need to invest more in multiple molecular dynamics simulations to quantify more accurately the structural behavior of the protein fragments in each pH study.

Os príons são proteínas que causam um grupo de doenças neurodegenerativas invariavelmente fatais, sendo uma das mais conhecidas a encefalopatia espongiforme bovina (ou doença da vaca louca). A proteína príon celular (PrPc), rica em estrutura α-helicoidal, sofre uma mudança na sua estrutura secundária produzindo a proteína patológica (PrPSc; o príon) na qual prevalecem folhas-β. Devido a falta de dados de estruturais de alta resolução dos príons, simulações de DM podem ser particularmente úteis para estudar o redobramento de PrP. Estudos experimentais e computacionais, descritos na literatura, indicam que a utilização de pH ácido é capaz de criar alguma instabilidade estrutural, produzindo um ganho de estrutura-β na região N-terminal antes desestruturada. Este trabalho se propõe a investigar computacionalmente as mudanças estruturais na proteína príon celular do hamster Sírio induzidas por alteração de pH. Para isso, foi avaliada a influência do uso de diferentes campos de força (GROMOS, AMBER e OPLS), diferentes estados de protonação dos resíduos de histidina, diferentes condições iniciais e diferentes métodos de cálculo de interações eletrostáticas de longo alcance (GRF e SPME). A partir da evolução temporal das estruturas secundárias, foi observada uma forte dependência dos resultados com o uso de diferentes parâmetros de simulação. De fato, a tendência de pH descrita na literatura não foi claramente observada neste trabalho. Isso pode estar associado com a necessidade de se investir mais em múltiplas simulações de dinâmica molecular para quantificar com maior precisão o comportamento estrutural dos fragmentos protéicos em cada pH de estudo. / Prions are proteins that cause a group of invariably fatal neurodegenerative diseases, one of the most known being bovine spongiform encephalopathy (or mad cow disease). The cellular prion protein (PrPc), rich in α-helical structure, undergoes a change in its secondary structure producing the pathological protein (PrPSc, the prion) in which β-sheet structure prevails. Because of the lack of high-resolution prion structural data, MD simulations can be particularly useful to study PrP misfolding. Experimental and computational studies, described in literature, indicate that the use of low pH is capable to create some structural instability, producing a gain of β-structure content in the otherwise unstructured N-terminal region. This work aims to investigate computationally structural changes in the cellular prion protein of Syrian hamster induced by pH change. For this, we evaluated the influence of different force fields (GROMOS, AMBER and OPLS), different protonation states of histidine residues, different initial conditions and different methods for calculating long-range electrostatic interactions (GRF and SPME). From the time evolution of the secondary structures, we observed a strong dependence on the simulation parameters. In fact, the pH tendency described in literature was not clearly observed in this work. It may be associated with the need to invest more in multiple molecular dynamics simulations to quantify more accurately the structural behavior of the protein fragments in each pH study.

Submitted by (ana.araujo@ufrpe.br) on 2016-08-04T14:28:53Z No. of bitstreams: 1 Maira de Oliveira Santos.pdf: 1516572 bytes, checksum: ea3508c7d99ef42591a6b17f459901e0 (MD5) / Made available in DSpace on 2016-08-04T14:28:53Z (GMT). No. of bitstreams: 1 Maira de Oliveira Santos.pdf: 1516572 bytes, checksum: ea3508c7d99ef42591a6b17f459901e0 (MD5) Previous issue date: 2010-06-07 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The study of climate has great economic end environmental importance, given that a single large and unexpected variation of a climatic element may devastate plantations or cities, and thus affect the economy of a region and life of the inhabitants. Climate can be influenced by diverse factors, such as latitude, altitude, air mass, proximity to sea, sea currents, terrain topology, vegetation, etc. The most important climate elements are temperature, humidity, atmospheric pressure, solar radiation, precipitation and wind. The wind is generated by atmospheric air mass movement, and may influence various phenomena such as soil erosion, pollutant dispersal, transport of pollen and seeds, propagation of diseases, as well as generation of eolic energy. Surface wind velocity is natural example of the phenomenon of turbulence, which represents a stochastic process characterized by temporal and spatial scale invariance. In this work we study long range correlations in temporal series of wind speed and direction registered at four meteorological stations in the cities of Arcoverde, Cabrobro, Garanhuns and Petrolina, in the state of Pernambuco, Brazil. To this end we apply Detrended Fluctuation Analysis (DFA) which was developed for quantification of long range correlations in non-stationary temporal series. We analyze the original wind speed series together with volatility (absolute value of increments) of the wind direction. All the analyzed series exhibit persistent long range correlations with the scale exponent above 0.5. In all cases the exponent values were found to be lower for wind direction then those for wind speed, indicating weaker persistence. No correlation was detected between the exponent values and the geographic parameters: longitutde, latitude and altitude of the station. The results of these analyses contribute to a better understanding of the nature of stochastic processes governing wind dynamics, necessary for development of more realistic theoretical and computational models as a base for modeling diverse phenomena influenced by climatic conditions. / O estudo do clima e dos seus elementos tem grande importância econômica e ambiental, visto que uma grande e inesperada variação em ao menos um dos elementos do clima pode devastar plantações, cidades, e assim mudar a economia de uma região e a vida das pessoas que ali habitam. O clima pode ser influenciado por diversos fatores, tais como latitude, altitude, massas do ar, continentalidade, maritmidade, correntes marítimas, relevo, vegetação, etc. Os elementos mais importantes do clima são temperatura, umidade, pressão atmosférica, radiação solar, precipitação e vento. O vento é gerado pelo movimento de massas do ar na atmosfera e pode influenciar vários fenômenos, como erosão do solo, dispersão de poluentes, transporte de pólen e sementes, propagação de doenças e geração da energia eólica. A velocidade do vento na superfície é um exemplo natural do fenômeno de turbulência, que representa um processo estocástico caracterizado pela invariância de escala temporal e espacial. Neste trabalho foram estudadas as correlações de longo alcance em séries temporais da velocidade e direção do vento registradas em quatro estações meteorológicas, nas cidades Arcoverde, Cabrobó, Garanhuns e Petrolina em Pernambuco. Foi utilizado o método Detrended fluctuation analysis (DFA), desenvolvido para quantificar as correlações de longo alcance em séries temporais não estacionárias. Foram analisadas as séries originais da velocidade do vento e as séries dos valores absolutos dos incrementos (volatilidade) da direção do vento. Todas as séries analisadas possuem as correlações de longo alcance persistentes, com expoente de escala acima de 0,5. Em todos os casos os valores dos expoentes são menores para a direção do que para a velocidade do vento, indicando que a persistência é mais fraca para a direção do vento. Não foi detectada a correlação entre os valores dos expoentes de escala e os parâmetros geográficos: longitude, latitude e altitude da estação. Os resultados destas análises vão ajudar a entender melhor a natureza dos processos estocásticos geradores da dinâmica do vento. Este entendimento é necessário para desenvolvimento dos modelos teóricos e computacionais mais precisos cujos resultados servirão como base para modelagem dos vários fenômenos influenciados pelas condições climáticas.

Submitted by (ana.araujo@ufrpe.br) on 2016-08-12T14:38:54Z No. of bitstreams: 1 Rosilda Benecio de Souza.pdf: 1979743 bytes, checksum: 6e2df03119bd441a84297bc73d2befeb (MD5) / Made available in DSpace on 2016-08-12T14:38:54Z (GMT). No. of bitstreams: 1 Rosilda Benecio de Souza.pdf: 1979743 bytes, checksum: 6e2df03119bd441a84297bc73d2befeb (MD5) Previous issue date: 2011-02-17 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / Vegetation and forest fires affect millions of hectares of Brazilian land and have severe ecological, social and economic consequences, including emissions of green house gases, loss of biodiversity, soil erosion etc. To establish efficient methods for prevention and suppression of fires, which is crucial for preservation of environment, it is necessarily to know the spatial location and time of occurrence of fires, burned area, why they occur, and how they initiate and propagate. Several satellite systems are currently available for monitoring different fire characteristics: dry areas that are susceptible to fire, actively flaming fires, burned area and smoke, and trace gas emissions. Hot pixels are satellite image pixels with infrared intensity corresponding to burning vegetation. Depending of image resolution, a hot pixel may represent one fire, or a part of a larger fire. Together with other satellite data, the number of hot pixels can be used to estimate the burned area and predict environmental and economics consequences. In this work we study the dynamics of hot pixels detected in Brazil by satellite NOAA-12 during the period 1998-2007, using the method Multifractal Detrended Fluctuation Analysis, which serves to detect and quantify multifractal properties of non-stationary temporal series. We calculate the generalized Hurst exponent h(q), Renyi exponent (q) and singularity spectrum f( ). The results show the existence of power-law long-term correlations that are described by a hierarchy of scaling exponents, which is the consequence of an underlying multifractal stochastic process. Based on this empirical result we also show that the Multifractal Cascade Model can be used to produce synthetic data for hot pixels dynamics. The observed multifractal property of temporal series of hot pixels should be incorporated in theoretical models and computer simulations of the fire dynamics and related phenomena. / Queimadas e incêndios florestais atingem milhões de hectares de terras brasileiras, causando graves consequências ecológicas, sociais e econômicas, incluindo emissões de gases do efeito estufa, perda de biodiversidade, erosão do solo, etc. Para estabelecer métodos eficientes para prevenção e supressão do fogo, importantes para proteção do meio ambiente, é necessário conhecer onde, quando e porquê os incêndios ocorrem, a área queimada e como se iniciam e se propagam. Atualmente, vários satélites são disponibilizados para monitoramento das características do fogo: áreas de risco, incêndios atualmente ativos, área queimada, fumaça e emissão de gases. Focos de calor são pixels na imagem de satélite, com intensidade infravermelha correspondente a vegetação queimada. Dependendo da resolução, um foco pode representar uma queimada ou parte de um incêndio maior. O número de focos combinado a outras informações fornecidas pelos satélites pode ser usado para estimar a área queimada, e prever as consequências ecológicas e econômicas. Neste trabalho, foi estudada a dinâmica de focos de calor detectados no Brasil pelo satélite NOAA-12, durante o período 1998-2007, utilizando o método Multifractal Detrended Fluctuation Analysis, desenvolvido para detecção e quantificação das propriedades mutifractais das séries temporais não estacionárias. Foram calculados o expoente generalizado de Hurst h(q), o expoente Renyi (q) e o espectro de singularidade f( ). Os resultados mostraram a existência de correlações de longo alcance, caracterizadas por uma hierarquia dos expoentes de escala, conseqüência de um processo estocástico multifractal. Baseado nos resultados empíricos, também foram mostrados que o Multifractal Cascade Model pode ser usado para gerar séries artificiais dos focos de calor. A propriedade multifractal da dinâmica dos focos de calor poderá ser incorporada em modelos teóricos e simulações computacionais de dinâmica de incêndios e fenômenos relacionados.