DOTA-based Ga(III) and Gd(III) chelates for medical imaging (PET, SPECT and MRI)

PhD Thesis in Sciences Specialization in Chemistry

The effects of solvent composition on the affinity of a peptide towards hair keratin: experimental and molecular dynamics data

The study of the interaction between hair filaments and formulations or peptides is of utmost importance in fields like cosmetic research. Keratin intermediate filaments structure is not fully described, limiting the molecular dynamics (MD) studies in this field although its high potential to improve the area. We developed a computational model of a truncated protofibril, simulated its behavior in alcoholic based formulations and with one peptide. The simulations showed a strong interaction between the benzyl alcohol molecules of the formulations and the model, leading to the disorganization of the keratin chains, which regress with the removal of the alcohol molecules. This behavior can explain the increase of peptide uptake in hair shafts evidenced in fluorescence microscopy pictures. The model developed is valid to computationally reproduce the interaction between hair and alcoholic formulations and provide a robust base for new MD studies about hair properties. It is shown that the MD simulations can improve hair cosmetic research, improving the uptake of a compound of interest.

Dielectric relaxation dynamics of high-temperature piezoelectric polyimide copolymers

Polyimide co-polymers have been prepared based on different diamines as co-monomers: a diamine without CN groups and a novel synthesized diamine with two CN groups prepared by polycondensation reaction followed by thermal cyclodehydration. Dielectric spectroscopy measurements were performed and the dielectric complex function, ac conductivity and electric modulus of the co-polymers were investigated as a function of CN group content in the frequency range from 0.1 Hz to 107 Hz at temperatures from 25 to 260 °C. For all samples and temperatures above 150ºC, the dielectric constant increases with increasing temperature due to increaseing conductivity. The α-relaxation is just detected for the sample without CN groups, being this relaxation overlapped by the electrical conductivity contributions in the remaining samples. For the copolymer samples and the polymer with CN groups an important Maxwell-Wagner-Sillars contribution is detected. The mechanisms responsible for the dielectric relaxation, conduction process and electric modulus response have been discussed as a function of the CN groups content present in the samples.

Population Dynamics Modeling of Arapaima gigas

Pirarucu (Arapaima gigas) has been of the most important natural fishing resources of the Amazon region. Due to its economic importance, and the necessity to preserve the species hand, field research concerning the habits and behavior of the pirarucu has been increasing for the last 20 years. The aim of this paper is to present a mathematical model for the pirarucu population dynamics considering the species peculiarities, particularly the male parental care over the offspring. The solution of the dynamical systems indicates three possible equilibrium points for the population. The first corresponds to extinction; the third corresponds to a stable population close to the environmental carrying capacity. The second corresponds to an unstable equilibrium located between extinction and full use of the carrying capacity. It is shown that lack of males’ parental care closes the gap between the point corresponding to the unstable equilibrium and the point of stable non-trivial equilibrium. If guarding failure reaches a critical point the two points coincide and the population tends irreversibly to extinction. If some event tends to destabilize the population equilibrium, as for instance inadequate parental care, the model responds in such a way as to restore the trajectory towards the stable equilibrium point avoiding the route to extinction. The parameters introduced to solve the system of equations are partially derived from limited but reliable field data collected at the Mamirauá Sustainable Development Reserve (MSDR) in the Brazilian Amazonian Region.

Symptoms and signs in rigid gas permeable lens wearers during adaptation period

Objectives: To evaluate neophyte contact lens wearers’ fitting to rigid gas permeable (RGP) contact lenses in terms of wearing time, tear volume, stability, corneal staining, and subjective ratings, over a 1-month period of time. Methods: Twenty-two young healthy subjects were enrolled for wearing RGP on a daily wear basis. The participants included in this study never wore contact lenses and showed a value under 10 in McMonnies Questionnaire. Contact Lens Dry Eye Questionnaire, Visual Analog Scales, Schirmer test, tear film break-up time (BUT), and corneal staining grading were performed. Follow-up visits were scheduled at 1, 7, 15, and 28 days. Results: Six subjects dropped out due to discomfort from the study before 1 month (27% of discontinuation rate). Successful RGP wearers (16 participants) achieved high levels of subjective vision and reported comfort scores of approximately 9 of 10 between 10 and 15 days. They reported wearing their lenses for an average of 10.1262.43 hr after 1 month of wear. Conversely, unsuccessful wearers discontinued wearing the lenses after the first 10 to 15 days, showing comfort scores and wearing time significantly lower compared with the first day of wear. Schirmer test showed a signifi- cant increase at 10 days (P,0.001), and the BUT trends decreased after the first week of wear in unsuccessful group. Conclusions: Symptomatology related with dryness and discomfort, detected during the first 10 days of the adaptation, may help the clinician to predict those participants who will potentially fail to adapt to RGP lens wear.

NF-kB pathway controls mitochondrial dynamics

The Optic atrophy 1 protein (OPA1) is a key element in the dynamics and morphology of mitochondria. We demonstrated that the absence of I?B kinase-a, which is a key element of the nonclassical NF-?B pathway, has an impact on the mitochondrial network morphology and OPA1 expression. In contrast, the absence of NF-?B essential modulator (NEMO) or I?B kinase-ß, both of which are essential for the canonical NF-?B pathway, has no impact on mitochondrial dynamics. Whereas Parkin has been reported to positively regulate the expression of OPA1 through NEMO, herein we found that PARK2 overexpression did not modify the expression of OPA1. PARK2 expression reduced the levels of Bax, and it prevented stress-induced cell death only in Bak-deficient mouse embryonic fibroblast cells. Collectively, our results point out a role of the nonclassical NF-?B pathway in the regulation of mitochondrial dynamics and OPA1 expression.

Flood pulse and spatial dynamics of mercury in sediments in Puruzinho lake, Brazilian Amazon

The study was conducted in Puruzinho lake (Humaitá, AM) considering seasonal periods of rainy and dry in way to elucidate the flood pulse importance in the deposition, remobilization and distributions of mercury and organic matter in bottom sediments in the Madeira River Basin (Brazilian Amazon). Bottom sediments and soils samples were analyzed for total mercury and organic matter. Mercury concentrations obtained in bottom sediment were 32.20-146.40 ng g-1 and organic matter values were 3.5 - 18.0%. The main region for accumulation of mercury and organic matter was in the central and deepest lake area In the rainy season there was a greater distribution of Hg and organic matter, mainly controlled by means of income of the Madeira river water during flooding, while the predominant process in the dry season was the remobilization of total Hg due to the resuspension of bottom sediments.

The influence of the conservation status and changes in the rainfall regime on forest-savanna mosaic dynamics in Northern Brazilian Amazonia

Coupled carbon/climate models are predicting changes in Amazon carbon and water cycles for the near future, with conversion of forest into savanna-like vegetation. However, empirical data to support these models are still scarce for Amazon. Facing this scenario, we investigated whether conservation status and changes in rainfall regime have influenced the forest-savanna mosaic over 20 years, from 1986 to 2006, in a transitional area in Northern Amazonia. By applying a spectral linear mixture model to a Landsat-5-TM time series, we identified protected savanna enclaves within a strictly protected nature reserve (Maracá Ecological Station - MES) and non-protected forest islands at its outskirts and compared their areas among 1986/1994/2006. The protected savanna enclaves decreased 26% in the 20-years period at an average rate of 0.131 ha year-1, with a greater reduction rate observed during times of higher precipitation, whereas the non-protected forest islands remained stable throughout the period of study, balancing the encroachment of forests into the savanna during humid periods and savannization during reduced rainfall periods. Thus, keeping favorable climate conditions, the MES conservation status would continue to favor the forest encroachment upon savanna, while the non-protected outskirt areas would remain resilient to disturbance regimes. However, if the increases in the frequency of dry periods predicted by climate models for this region are confirmed, future changes in extension and directions of forest limits will be affected, disrupting ecological services as carbon storage and the maintenance of local biodiversity.

Electronic structure and optical signatures of semiconducting transition metal dichalcogenide nanosheets

CONSPECTUS: Two-dimensional (2D) crystals derived from transition metal dichalcogenides (TMDs) are intriguing materials that offer a unique platform to study fundamental physical phenomena as well as to explore development of novel devices. Semiconducting group 6 TMDs such as MoS2 and WSe2 are known for their large optical absorption coefficient and their potential for high efficiency photovoltaics and photodetectors. Monolayer sheets of these compounds are flexible, stretchable, and soft semiconductors with a direct band gap in contrast to their well-known bulk crystals that are rigid and hard indirect gap semiconductors. Recent intense research has been motivated by the distinct electrical, optical, and mechanical properties of these TMD crystals in the ultimate thickness regime. As a semiconductor with a band gap in the visible to near-IR frequencies, these 2D MX2 materials (M = Mo, W; X = S, Se) exhibit distinct excitonic absorption and emission features. In this Account, we discuss how optical spectroscopy of these materials allows investigation of their electronic properties and the relaxation dynamics of excitons. We first discuss the basic electronic structure of 2D TMDs highlighting the key features of the dispersion relation. With the help of theoretical calculations, we further discuss how photoluminescence energy of direct and indirect excitons provide a guide to understanding the evolution of the electronic structure as a function of the number of layers. We also highlight the behavior of the two competing conduction valleys and their role in the optical processes. Intercalation of group 6 TMDs by alkali metals results in the structural phase transformation with corresponding semiconductor-to-metal transition. Monolayer TMDs obtained by intercalation-assisted exfoliation retains the metastable metallic phase. Mild annealing, however, destabilizes the metastable phase and gradually restores the original semiconducting phase. Interestingly, the semiconducting 2H phase, metallic 1T phase, and a charge-density-wave-like 1T' phase can coexist within a single crystalline monolayer sheet. We further discuss the electronic properties of the restacked films of chemically exfoliated MoS2. Finally, we focus on the strong optical absorption and related exciton relaxation in monolayer and bilayer MX2. Monolayer MX2 absorbs as much as 30% of incident photons in the blue region of the visible light despite being atomically thin. This giant absorption is attributed to nesting of the conduction and valence bands, which leads to diversion of optical conductivity. We describe how the relaxation pathway of excitons depends strongly on the excitation energy. Excitation at the band nesting region is of unique significance because it leads to relaxation of electrons and holes with opposite momentum and spontaneous formation of indirect excitons.

Influence of the hip joint modeling approaches on the kinematics of human gait

The influence of the hip joint formulation on the kinematic response of the model of human gait is investigated throughout this work. To accomplish this goal, the fundamental issues of the modeling process of a planar hip joint under the framework of multibody systems are revisited. In particular, the formulations for the ideal, dry, and lubricated revolute joints are described and utilized for the interaction of femur head inside acetabulum or the hip bone. In this process, the main kinematic and dynamic aspects of hip joints are analyzed. In a simple manner, the forces that are generated during human gait, for both dry and lubricated hip joint models, are computed in terms of the system’s state variables and subsequently introduced into the dynamics equations of motion of the multibody system as external generalized forces. Moreover, a human multibody model is considered, which incorporates the different approaches for the hip articulation, namely ideal joint, dry, and lubricated models. Finally, several computational simulations based on different approaches are performed, and the main results presented and compared to identify differences among the methodologies and procedures adopted in this work. The input conditions to the models correspond to the experimental data capture from an adult male during normal gait. In general, the obtained results in terms of positions do not differ significantly when the different hip joint models are considered. In sharp contrast, the velocity and acceleration plotted vary significantly. The effect of the hip joint modeling approach is clearly measurable and visible in terms of peaks and oscillations of the velocities and accelerations. In general, with the dry hip model, intra-joint force peaks can be observed, which can be associated with the multiple impacts between the femur head and the cup. In turn, when the lubricant is present, the system’s response tends to be smoother due to the damping effects of the synovial fluid.

External and internal dynamics in the EU's counter-terrorism policy: a political and legal analysis

Tese de Doutoramento em Ciência Política e Relações Internacionais

Nanocomposites: the contribution of multiscale modelling to improve the dispersion levels

Tese de Doutoramento em Ciência e Engenharia de Polímeros e Compósitos

A bio-inspired computational model for motion detection

Tese de Doutoramento (Programa Doutoral em Engenharia Biomédica)

Using mouse dynamics to assess stress during online exams

"Lecture notes in computer science series", ISSN 0302-9743, vol. 9121

Angular velocity and acceleration

In this chapter, a complete characterization of the angular velocity and angular acceleration for rigid bodies in spatial multibody systems are presented. For both cases, local and global formulations are described taking into account the advantages of using Euler parameters. In this process, the transformation between global and local components of the angular velocity and time derivative of the Euler parameters are analyzed and discussed in this chapter.