Dispersion and re-agglomeration of graphite nanoplates in polypropylene melts under controlled flow conditions

The kinetics of GnP dispersion in polypropylene melt was studied using a prototype small scale modular extensional mixer. Its modular nature enabled the sequential application of a mixing step, melt relaxation, and a second mixing step. The latter could reproduce the flow conditions on the first mixing step, or generate milder flow conditions. The effect of these sequences of flow constraints upon GnP dispersion along the mixer length was studied for composites with 2 and 10 wt.% GnP. The samples collected along the first mixing zone showed a gradual decrease of number and size of GnP agglomerates, at a rate that was independent of the flow conditions imposed to the melt, but dependent on composition. The relaxation zone induced GnP re-agglomeration, and the application of a second mixing step caused variable dispersion results that were largely dependent on the hydrodynamic stresses generated.

Improvign mixing processes with the help of numerical tools

In several industrial applications, highly complex behaviour materials are used together with intricate mixing processes, which difficult the achievement of the desired properties for the produced materials. This is the case of the well-known dispersion of nano-sized fillers in a melt polymer matrix, used to improve the nanocomposite mechanical and/or electrical properties. This mixing is usually performed in twin-screw extruders, that promote complex flow patterns, and, since an in loco analysis of the material evolution and mixing is difficult to perform, numerical tools can be very useful to predict the evolution and behaviour of the material. This work presents a numerical based study to improve the understanding of mixing processes. Initial numerical studies were performed with generalized Newtonian fluids, but, due to the null relaxation time that characterize this type of fluids, the assumption of viscoelastic behavior was required. Therefore, the polymer melt was rheologically characterized, and, a six mode Phan-Thien-Tanner and Giesekus models were used to fit the rheological data. These viscoelastic rheological models were used to model the process. The conclusions obtained in this work provide additional and useful data to correlate the type and intensity of the deformation history promoted to the polymer nanocomposite and the quality of the mixing obtained.

Otimização com restrições de complementaridade: algoritmos e aplicações

Tese de Doutoramento em Engenharia Industrial e de Sistemas (PDEIS)

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

PhD Thesis in Sciences Specialization in Chemistry

Fine time scaling of purifying selection on human nonsynonymous mtDNA mutations based on the worldwide population tree and mother-child pairs

A high-resolution mtDNA phylogenetic tree allowed us to look backward in time to investigate purifying selection. Purifying selection was very strong in the last 2,500 years, continuously eliminating pathogenic mutations back until the end of the Younger Dryas (∼11,000 years ago), when a large population expansion likely relaxed selection pressure. This was preceded by a phase of stable selection until another relaxation occurred in the out-of-Africa migration. Demography and selection are closely related: expansions led to relaxation of selection and higher pathogenicity mutations significantly decreased the growth of descendants. The only detectible positive selection was the recurrence of highly pathogenic nonsynonymous mutations (m.3394T>C-m.3397A>G-m.3398T>C) at interior branches of the tree, preventing the formation of a dinucleotide STR (TATATA) in the MT-ND1 gene. At the most recent time scale in 124 mother-children transmissions, purifying selection was detectable through the loss of mtDNA variants with high predicted pathogenicity. A few haplogroup-defining sites were also heteroplasmic, agreeing with a significant propensity in 349 positions in the phylogenetic tree to revert back to the ancestral variant. This nonrandom mutation property explains the observation of heteroplasmic mutations at some haplogroup-defining sites in sequencing datasets, which may not indicate poor quality as has been claimed.

PEGylated DOTA-AHA-based Gd(III) chelates – A relaxometric study

Three PEGylated derivatives of 1,4,7,10-tetraazacyclododecane-1-((6-amino)hexanoic)-4,7,10-triacetic acid) (DOTA-AHA) with different molecular weights were prepared and characterized. Their Gd(III) chelates were studied in aqueous solution using variable-temperature 1H nuclear magnetic relaxation dispersion (NMRD) and 17ONMR spectroscopy in view of the determination of their relaxivity and the parameters that govern it. The relaxivity varied from 5.1 to 6.5 mM-1.s-1 (37 ºC and 60 MHz) with the increasing molecular weight of the PEG chain, being slightly higher than that of the parent chelate Gd(DOTA-AHA), due to a small contribution of a slow global rotation of the complexes. A variable temperature 1H NMR study of several Ln(III) chelates of DOTA-A(PEG750)HA allowed the determination of the isomeric M/m ratio (M = square antiprismatic isomer and m = twisted square antiprismatic isomer, the latter presenting a much faster water exchange) which for the Gd(III) chelate was estimated in circa 1:0.2, very close to that of [Gd(DOTA)]-. This explains why the PEGylated Gd(III) chelate has a water rate exchange similar to that of [Gd(DOTA)]-. The predominance of the M isomer is a consequence of the bulky PEG moiety which does not favor the stabilization of the m isomer in sterically crowded systems at the substituent site, contrary to what happens with less packed asymmetrical DOTA-type chelates with substitution in one of the four acetate C(α) atoms.

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.

Cardio-respiratory symptoms in panic disorder: a contribution from cognitive-behaviour therapy

Objective: To compare patients with panic disorder with agoraphobia treated with cognitive-behavioural therapy (CBT) associated with the medication with patients treated only with medication and verify the behaviour of the cardio-respiratory symptoms of both groups. Methods: Randomized sample in the Psychiatry Institute of the Federal University of Rio de Janeiro, divided in two groups of 25 participants each. Group 1 undertook 10 weekly sessions of CBT with one hour of duration each together with medication. Group 2, Control, were administered medication that only consisted of tricyclic anti-depressants and selective inhibitors of the re-uptake of serotonin. Evaluation instruments were applied at the beginning and to the end of the interventions. Results: According to the applied scales, group 1 showed statistically more significant results than group 2, with: reduction of panic attacks, cardio-respiratory symptoms, anticipatory anxiety, agoraphobia avoidance and fear of bodily sensations. Conclusion: Exposures (in vivo and interoceptive), especially for induction symptom exercises and relaxation, were considered essential to prepare patients with panic disorder to handle future cardio-respiratory symptoms and panic attacks with agoraphobia.

Development and characterization of lipid-based nanosystems for controlled release of bioactive compounds

Tese de Doutoramento em Engenharia Química e Biológica.

Rheological characterization of EVA and HDPE polymer modified bitumens under large deformation at 20 º C

Large amplitude oscillatory shear (LAOS) coupled with Fourier transform rheology (FTR) was used for the first time to characterize the large deformation behavior of selected bituminous binders at 20 C. Two polymer modified bitumens (PMB) containing recycled EVA and HDPE and two unmodified bitumens were tested with LAOS-FTR. The LAOS-FTR response of all binders was compared at same frequency, at same Deborah number (by tuning the frequency to the relaxation time of each binder) and at same phase shift angle d (by tuning the frequency to the one corresponding to d = 50 in the SAOS response of each sample). In all the approaches, LAOS-FTR results allowed to differentiate between all the nonlinear mechanical characteristics of the tested binders. All binders show LAOS-FTR patterns reminiscent from colloidal dispersions and emulsions. EVA PMB was less prone to strain-induced microstructural changes when compared to HDPE PMB which showed larger values of nonlinear FTR parameters for the range of shear strains tested in LAOS.

Fluência no betão desde as primeiras idades: um estudo experimental

Dissertação de mestrado integrado em Engenharia Civil

Encapsulation and controlled release of bioactive compounds in lactoferrin-glycomacropeptide nanohydrogels : curcumin and caffeine as model compounds

Curcumin and caffeine (used as lipophilic and hydrophilic model compounds, respectively) were successfully encapsulated in lactoferrin-glycomacropeptide (Lf-GMP) nanohydrogels by thermal gelation showing high encapsulation efficiencies (>90 %). FTIR spectroscopy confirmed the encapsulation of bioactive compounds in Lf-GMP nanohydrogels and revealed that according to the encapsulated compound different interactions occur with the nanohydrogel matrix. The successful encapsulation of bioactive compounds in Lf-GMP nanohydrogels was also confirmed by fluorescence measurements and confocal laser scanning microscopy. TEM images showed that loaded nanohydrogels maintain their spherical shape with sizes of 112 and 126 nm for curcumin and caffeine encapsulated in Lf-GMP nanohydrogels, respectively; in both cases a polydispersity of 0.2 was obtained. The release mechanisms of bioactive compounds through Lf-GMP nanohydrogels were evaluated at pH 2 and pH 7, by fitting the Linear Superimposition Model to the experimental data. The bioactive compounds release was found to be pH-dependent: at pH 2, relaxation is the governing phenomenon for curcumin and caffeine compounds and at pH 7 Ficks diffusion is the main mechanism of caffeine release while curcumin was not released through Lf-GMP nanohydrogels.

Effects of protein-calorie restriction on mechanical function of hypertrophied cardiac muscle

OBJECTIVE: To assess the effect of food restriction (FR) on hypertrophied cardiac muscle in spontaneously hypertensive rats (SHR). METHODS: Isolated papillary muscle preparations of the left ventricle (LV) of 60-day-old SHR and of normotensive Wistar-Kyoto (WKY) rats were studied. The rats were fed either an unrestricted diet or FR diet (50% of the intake of the control diet) for 30 days. The mechanical function of the muscles was evaluated through monitoring isometric and isotonic contractions. RESULTS: FR caused: 1) reduction in the body weight and LV weight of SHR and WKY rats; 2) increase in the time to peak shortening and the time to peak developed tension (DT) in the hypertrophied myocardium of the SHR; 3) diverging changes in the mechanical function of the normal cardiac muscles of WKY rats with reduction in maximum velocity of isotonic shortening and of the time for DT to decrease 50% of its maximum value, and increase of the resting tension and of the rate of tension decline. CONCLUSION: Short-term FR causes prolongation of the contraction time of hypertrophied muscles and paradoxal changes in mechanical performance of normal cardiac fibers, with worsening of the shortening indices and of the resting tension, and improvement of the isometric relaxation.

Doppler echocardiographic evaluation of HIV-positive patients in different stages of the disease

OBJETIVE: To evaluate by Doppler echocardiography (DE) early abnormalities of ventricular function in HIV-positive patients, as well as other cardiac abnormalities that can be detected by this method, with special emphasis on mitral valve flow. METHODS: 84 HIV- positive patients, 59 with CD4 cell count >500/mm³ (Group A) and 25 with CD4 cell count <500/mm³ (Group B), were analyzed. CD4 cells were counted and matched with structural data and systolic and diastolic function of the left ventricle (LV), as analyzed by DE. The results were compared with those obtained in 47 healthy individuals (Group C). RESULTS: 8% of patients in Group B had mild pericardial effusion; 31.5% showed decreased systolic function of the LV, and 12% had moderate mitral regurgitation. A wave velocity from the mitral inflow was different among the 3 groups, being higher in Group B, where the deceleration time of the E wave of the mitral inflow and the E/A ratio were significantly lower with a normal value of the isovolumic relaxation time (IVRT). CONCLUSION: HIV-positive patients with a CD4 cell count >500/mm³ had no abnormalities by DE. Patients with a more advanced infection (those with a CD4 cell count <500/mm³), had a significantly abnormal LV systolic function and a higher incidence of pericardial effusion and mitral regurgitation. Mitral valve inflow by Doppler did not indicate diastolic dysfunction.

Influence of chitosan coating on protein-based nanohydrogels properties and in vitro gastric digestibility

Chitosan coating was applied in Lactoferrin (Lf)-Glycomacropeptide (GMP) nanohydrogels by layer-by-layer coating process. A volume ratio of 0.1 of Lf-GMP nanohydrogels (0.2 mg.mL-1, at pH 5.0) to chitosan (1 mg.mL-1, at pH 3) demonstrated to be the optimal condition to obtain stable nanohydrogels with size of 230 ± 12 nm, a PdI of 0.22 ± 0.02 and a -potential of 30.0 ± 0.15 mV. Transmission electron microscopy (TEM) images showed that the application of chitosan coating in Lf-GMP did not affect the spherical shape of nanohydrogels and confirmed the low aggregation of nanohydrogels in solution. The analysis of chemical interactions between chitosan and Lf-GMP nanohydrogels were performed by Fourier transform infrared spectroscopy (FTIR) and by circular dichroism (CD) that revealed that a specific chemical interaction occurring between functional groups of protein-based nanohydrogels and active groups of the chitosan was established. The effect of chitosan coating on release mechanisms of Lf-GMP nanohydrogels at acid conditions (pH 2, 37 ºC) was evaluated by the encapsulation of a model compound (caffeine) in these systems. Linear Superposition Model was used to fit the experimental data and revealed that Fick and relaxation mechanisms are involved in caffeine release. It was also observed that the Fick contribution increase with the application of chitosan coating. In vitro gastric digestion was performed with Lf-GMP nanohydrogels and Lf-GMP nanohydrogels with chitosan coating and it was observed that the presence of chitosan improve the stability of Lf and GMP (proteins were hydrolysed at a slower rate and were present in solution by longer time). Native electrophoreses revealed that the nanohydrogels without coating remained intact in solution until 15 min and with chitosan coating remained intact until 60 min, during gastric digestion.