Associations between intensive diabetes therapy and NMR-determined lipoprotein subclass profiles in Type 1 diabetes

Our objective is to define differences in circulating lipoprotein subclasses between intensive vs. conventional management of Type 1 diabetes during the randomization phase of the Diabetes Control and Complications Trial (DCCT). Nuclear magnetic resonance-determined lipoprotein subclass profiles (NMR-LSP), which estimate molar subclass concentrations and mean particle diameters, were determined in 1,294 DCCT subjects after a median of five (interquartile range: four, six) years following randomization to intensive or conventional diabetes management. In cross-sectional analyses, we compared standard lipids and NMR-LSP between treatment groups. Standard total-, LDL- and HDL-cholesterol levels were similar between randomization groups, while triglyceride levels were lower in the intensively treated group. NMR-LSP showed that intensive therapy was associated with larger LDL diameter (20.7 vs. 20.6 nm, p=0.01) and lower levels of small LDL (median: 465 vs. 552 nmol/l, p=0.007), total IDL/LDL (mean: 1000 vs. 1053 nmol/l, p=0.01), and small HDL (mean: 17.3 vs. 18.6 μmol/l, p<0.0001), the latter accounting for reduced total HDL (mean: 33.8 vs. 34.8 μmol/l, p=0.01). In conclusion, intensive diabetes therapy was associated with potentially favorable changes in LDL and HDL subclasses in sera. Further research will determine whether these changes contribute to the beneficial effects of intensive diabetes management on vascular complications.

Surface spin disorder in nickel ferrite nanomagnets studied by in-field Mossbauer spectroscopy

The magnetic structure of NiFe(2)O(4) nanoparticles has been investigated by means of Mossbauer spectra at T=4.2 K in applied fields up to 12 T. Four samples were studied, with mean particle diameters ranging from 4.3 to 8.9 nm. All spectra could be decomposed into three sextets, two corresponding to the ferrimagnetic sublattices of Fe ions in the spinel structure (core) and the third one to randomly frozen spins near the particle surface (shell). The shell thickness, calculated from the fraction of disordered spins, was found to be about one-third of the particle radius at H (app)=e0 and to decrease with the applied field toward a common limit of similar to 0.4 nm. The mean canting angle relative to the field was also found to decrease for increasing fields, at a rate inversely correlated to the particle size.

Thinning of a vertical free draining aqueous film incorporating colloidal particles

The drainage under gravity of a vertical foam film formed on a wire frame has been investigated. Dual-wavelength optical interferometry was used so that unambiguous fringe order assignments could be made, enabling absolute film thicknesses to be calculated with confidence. Films were stabilized by nonionic polypropylene glycol surfactant. Halfmicrometer silica particles with varying degrees of hydrophobicity were added to the film-forming liquid to investigate their effect on film drainage rate and stability. Hydrophilic particles had little or no effect, while hydrophobic particles slowed the drainage of the film and caused a minor increase in film lifetime, from ∼10 to ∼30 s. In both the hydrophilic and hydrophobic cases the films ruptured when they reached a thickness of ∼2 particle diameters. Particles of intermediate hydrophobicity had the most significant effect, increasing film lifetime by an order of magnitude over that for hydrophilic particles. The intermediate particles allowed films to thin down to a thickness less than the particle diameter, indicating that particles bridge across the entire film. This did not occur with more hydrophobic particles even though they were embedded in each of the two film surfaces. These results correlate well with previous literature on particle-laden foams. The film thickness and drainage measurements allow drainage mechanisms for the different particles to be identified, thus providing a mechanistic explanation for the observation by several previous authors that foams formed in the presence of particles, for example during mineral processing, have the greatest stability when the particles are of intermediate hydrophobicity.

Characterization of Atrazine-Loaded Biodegradable Poly(Hydroxybutyrate-Co-Hydroxyvalerate) Microspheres

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

Adição de areia para dispersão de solos na análise granulométrica

A acurácia da análise granulométrica depende da obtenção de suspensões de solo completamente dispersas e estáveis para possibilitar a separação das suas frações granulométricas. O objetivo do presente trabalho foi avaliar a eficácia da adição de quantidades e tamanhos de grãos de areia na fase de dispersão da análise granulométrica de solos, visando à maior acurácia na obtenção dos resultados da análise granulométrica. Os solos utilizados foram: Latossolo Vermelho eutroférrico (LVef), LatossoloVermelho acriférrico (LVwf), Latossolo Vermelho eutrófico (LVe), Argissolo Vermelho-Amarelo eutrófico (PVAe) e Nitossolo Vermelho eutroférrico (NVef). A dispersão das amostras dos solos foi realizada por meio da adição de hidróxido de sódio e agitação rotativa (60 rpm) por 16 h. O delineamento experimental adotado foi o inteiramente casualizado, com esquema fatorial 6 x 2, com três repetições. Os tratamentos foram constituídos por seis quantidades (0, 5, 10, 15, 20 e 25 g) e dois diâmetros (2,0-1,0 e 1,0-0,5 mm) de areia, adicionados na fase de dispersão da análise granulométrica dos solos. de acordo com as equações ajustadas, a adição de areia com diâmetro entre 1,0 e 0,5 mm nas quantidades de 21,4 g para LVef, 19,6 g para LVwf e 25,8 g para NVef proporciona, respectivamente para esses solos, aumentos de 50, 38 e 14,5 % nos teores de argila. No LVe e no PVAe não se justifica a adição de areia na análise granulométrica, pois esses solos não apresentaram problemas de dispersão. Os resultados demonstram que a adição de 25 g de areia, com diâmetro entre 1,0 e 0,5 mm, na fase de dispersão da análise granulométrica de solos argilosos com altos teores de óxidos de Fe e com dificuldades de dispersão, é eficiente para promover efetiva dispersão das partículas primárias do solo.

Suco desidratado de caju (Anacardium occidentale L.) por atomização: caracterização físico-química, bioativa e estudo da vida de prateleira do produto

Despite the relatively organized cashew (Anacardium occidentale L.) productive chain and the number of cashew derivatives found in the market, it is estimated that over 90% of the cashew peduncle is wasted. A possible strategy for a better commercial exploitation of this agroindustrial commodity would be the production of spray dried cashew pulp. Thus, this paper approaches the yellow cashew pulp spray drying process and the final product evaluation. Based on that, the shelf life of the spray dried cashew pulp packed in different packaging was evaluated. Drying was conducted in two drying temperatures (140 °C to 150 °C) and two concentrations of Arabic gum (AG, 15% and 25%), which summed four experimental groups. The drying performance was evaluated as well as the physicochemical characteristics (moisture, water activity, total soluble solids, pH, density, solubility, particle diameter, hygroscopicity, degree of caking, color, scanning electronic microscopy and X-ray diffraction), composition (protein, ash, fat and sugars) and bioactive and functional value (total phenolic compounds, carotenoids, ascorbic acid and antioxidant activity) of the final products. Results showed spray drying efficiency higher than 65% for all experiments, mainly for the C4 group (150 °C and 25% AG) which reached efficiency of 93.4%. It was also observed high solubility (94.7% to 97.9%) and the groups with lower hygroscopicity (5.8% and 6.5%) were those with the highest proportion of drying coadjuvant. The particle diameters ranged between 14.7 μm and 30.2 μm and increased with the proportion of AG. When comparing the product before and after spray drying, the drying impact was evident. However, despite the observed losses, dried yellow cashew showed high phenolic concentration (from 235.9 to 380.4 mg GAE eq / 100 g DM), carotenoids between 0.22 and 0.49 mg/100 g DM and remarkable ascorbic acid levels (852.4 to 1346.2 mg/100 g DM), in addition to antioxidant activity ranging from 12.9 to 16.4 μmol TE/ g DM. The shelf life study revealed decreased phenolic content over time associated to a slight water activity increase. Overall, our results unveil the technological and bioactive potential of dried yellow cashew as a functional ingredient to be used in food formulations or as a ready-to-use product. The technological approach presented here can serve as an efficient strategy for a rational use of the cashew apple, avoiding its current underutilization

Alginate-chitosan systems: In vitro controlled release of triamcinolone and in vivo gastrointestinal transit

The aim of this study was to develop multiparticulate therapeutic systems of alginate (AL) and chitosan (CS) containing triamcinolone (TC) to colonic drug delivery. Multiparticulate systems of AL-CS, prepared by a complex coacervation/ionotropic gelation method, were characterized for morphological and size aspects, swelling degree, encapsulation content and efficiency, in vitro release profile in different environments simulating the gastrointestinal tract (GIT) and in vivo gastrointestinal transit. The systems showed suitable morphological characteristics with particle diameters of approximately 1.6 mm. In simulated gastric environment, at pH 1.2, the capsules presented low degree of swelling and in vitro release of drug. A higher swelling degree was observed in simulated enteric environment, pH 7.5, followed by erosion. Practically all the drug was released after 6 h of in vitro assay. The in vivo analysis of gastrointestinal transit, carried out in rats, showed that the systems passed practically intact through the stomach and did not show the same profile of swelling observed in the in vitro tests. It was possible to verify the presence of capsules in the colonic region of GIT. The results indicate that AL-CS multiparticulate systems can be used as an adjuvant for the preparation of therapeutic systems to colonic delivery of drugs. (C) 2010 Elsevier Ltd. All rights reserved.

Nova proposta de critério de retenção para dimensionamento de filtros têxteis

The designs of filters made by granular material or textile are mainly based on empirical or semi empirical retention criteria according to Terzaghi proposal, which compares particle diameter of the soil base with the filter porous spaces. Silveira in 1965, proposed one rational design retention criteria based on the probability of a particle from the soil base, carried by one dimensional flow, be restrained by the porous of the filter while trying to pass through its thickness. This new innovating theory, besides of being very simple, it is not frequently used for granular filters since the necessary parameters for the design has to be determine for each natural material. However, for textile this problem no longer exists because it has quality control during manufacturing and the necessary characteristics properties of the product are specify in the product catalog. This work presents one adaptation of the Silveira theory for textile filters and the step-by-step procedure for the determination of the characteristics properties of the textile products necessary for the design. This new procedure permits the determination of the confiability level of retention that one specific particle diameter form the soil base has for one specified textile. One complete example is presented to demonstrate the simplicity of the method proposed and how the textile characteristics are obtained.

Determination of minimum fluidization velocity for gas-solid beds by experimental data and numerical simulations

The purpose of this work is to predict the minimum fluidization velocity Umf in a gas-solid fluidized bed. The study was carried out with an experimental apparatus for sand particles with diameters between 310μm and 590μm, and density of 2,590kg/m3. The experimental results were compared with numerical simulations developed in MFIX (Multiphase Flow with Interphase eXchange) open source code [1], for three different sizes of particles: 310mum, 450μm and 590μm. A homogeneous mixture with the three kinds of particles was also studied. The influence of the particle diameter was presented and discussed. The Ergun equation was also used to describe the minimum fluidization velocity. The experimental data presented a good agreement with Ergun equation and numerical simulations. Copyright © 2011 by ASME.

Ethanol electro-oxidation in an alkaline medium using Pd/C, Au/C and PdAu/C electrocatalysts prepared by electron beam irradiation

Carbon-supported Pd, Au and bimetallic PdAu (Pd:Au 90:10, 50:50 and 30:70 atomic ratios) electrocatalysts were prepared using electron beam irradiation. The obtained materials were characterized by energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD) and transmission electron microscopy (TEM), and their catalytic activities toward ethanol electro-oxidation were evaluated in an alkaline medium using electrochemical techniques, in situ attenuated total reflectance Fourier transformed infrared spectroscopy (ATR-FTIR) analysis and a single alkaline direct ethanol fuel cell (ADEFC). EDX analyses showed that the actual Pd: Au atomic ratios were very similar to the nominal ones. X-ray diffractograms of PdAu/C electrocatalysts evidenced the presence of Pd-rich (fcc) and Au-rich (fcc) phases. TEM analysis showed a homogeneous dispersion of nanoparticles on the carbon support, with an average size in the range of 3-5 nm and broad size distributions. Cyclic voltammetry (CV) and chronoamperometry (CA) experiments revealed the superior ambient activity toward ethanol electro-oxidation of PdAu/C electrocatalysts with Pd: Au ratios of 90:10 and 50:50. In situ ATR-FTIR spectroscopy measurements have shown that the mechanism for ethanol electro-oxidation is dependent on catalyst composition, leading to different reaction products, such as acetaldehyde and acetate, depending on the number of electrons transferred. Experiments on a single ADEFC were conducted between 50 and 900 C, and the best performance of 44 mW cm-2 in 2.0molL-1 ethanol was obtained at 850C for the Pd:Au 90:10 catalysts. This superior performance is most likely associated with enhancement of ethanol adsorption on Pd, oxidation of the intermediates, the presence of gold oxide-hydroxyl species, low mean particle diameters and better distribution of particles on the support. © 2013 Elsevier Ltd. All rights reserved.

Estudo da emissão e do controle dos gases e particulados provenientes da queima de biomassa

Pós-graduação em Engenharia Mecânica - FEG

Study of combustion of different biomass and its atmospheric emissions

One of the energy alternatives that provide utility, flexibility, cleanliness and economy is biomass, such as forest waste (wood) and agricultural (sugarcane bagasse, rice husks, coffee pods, etc.). However, with its increasing supply and use grows also the concern of industries to invest in monitoring and control of emissions into the atmosphere, because during biomass burning are emitted as exhaust gases, fine particles known as particulates, which greatly contribute to the triggering of serious health problems to humans, in addition to the environmental damage. With that, this work aimed to conduct a monitoring of particulate and gaseous pollutants emissions to the atmosphere from the burning of various types of biomass used by industries. The equipment used for sampling were the optical monitor DataRAM 4 and the Unigas3000 + gas sampler. The results showed that biomass coffee pods presented the greatest concentration of particulates (485119 μg m-3) with particle diameters between 0.0602 μm and 0.3502 μm, i.e. the most ultrafine particles, harmful to human health and the environment. The largest emissions of CO and NOx were observed, respectively, for the coffee pods (3500 ppm) and for the rice husk (48 ppm). As for the superior calorific value (PCS), the best of fuel, with higher PCS, was the Eucalyptus grandis.

Synthese von amphiphilen Bürstenpolymeren mit Kern-Schale-Architektur und Untersuchungen zur Verkapselung von hydrophilen Modellsubstanzen

Die dieser Arbeit zugrundeliegenden Nanopartikel wurden mittels der Makromonomer-Strategie aus polymerisierbaren Polystyrol-b-Poly(2-vinylpyridin) Oligomeren dargestellt. Die Bürstenpolymere besitzen eine polare PS-Schale und einen polaren Kern (P2VP), dessen Polarität durch Quaternisierung deutlich erhöht werden kann. Die Bürstenpolymere weisen bei Molmassen um 400 - 800 kg/mol einen Teilchendurchmesser von ca. 15 - 20 nm auf. Die Nanopartikel eignen sich dazu, hydrophile Farbstoffe in unpolaren Lösungsmitteln zu solubilisieren. Durch spektroskopische Untersuchungen wurden in Abhängigkeit der chemischen Struktur und der Bürstenpolymere Beladungsgrade von über 1 g Farbstoff pro Gramm Polymer ermittelt. Die Beladung der Nanopartikel folgt hierbei einer nichttrivialen Kinetik, was möglicherweise durch eine wasserinduzierte Überstrukturbildung während der Beladung bedingt ist. Mittels isothermer Titrationskalorimetrie konnten die Wechselwirkungen zwischen polymeren Substrat und niedermolekularen Liganden genauer charakterisiert werden. Teilweise werden hierbei zweistufige Titrationsverläufe und "überstöchiometrische" Beladung der Bürstenpolymere beobachtet. Den Hauptbeitrag zur Wechselwirkung liefert hierbei die exotherme Wechselwirkung zwischen basischen Polymer und saurem Farbstoff. Die hohe Farbstoffbeladung führt zur deutlichen Vergrößerung der einzelnen Nanopartikel, was sowohl in Lösung durch Lichtstreu-Techniken als auch auf Oberflächen mit Hilfe des AFM zu beobachten ist. Durch Untersuchungen mit der analytischen Ultrazentrifuge konnte nachgewiesen werden, dass sich der eingelagerte Farbstoff in einem Polaritäts-abhängigen Gleichgewicht mit der Umgebung steht, er somit auch wieder aus den Nanopartikeln freigesetzt werden kann. Darüberhinaus wurden im Rahmen der Arbeit erste Erfolge bei der Synthese von wasserlöslichen Nanopartikeln mit Poly(2-vinylpyridin)-Kern erzielt. Als hierfür geeignet stellte sich eine Synthesestrategie heraus, bei der zunächst ein Bürstenpolymer mit P2VP-Seitenketten dargestellt und dieses anschließend mit geeignet funktionalisierten Polyethylenoxid-Ketten zum Kern-Schale Teilchen umgesetzt wurde. Neben Untersuchungen zum Mizellisierungsverhalten von PEO-b-P2VP Makromonomeren wurden deren Aggregate in Wasser hinsichtlich ihrer Zelltoxizität durch in-vitro Experimente an C26-Mäusekarzinom-Zellen charakterisiert. Die extrem geringe Toxizität macht das PEO-P2VP System zu einem potentiellen Kandidaten für drug-delivery Anwendungen. Besonders die pH-abhängige Löslichkeitsänderung des Poly(2-vinylpyridin) erscheint hierbei besonders interessant.

Mechanical microcontacts of powder particles studied with the quartz crystal microbalance

Within this work, a particle-polymer surface system is studied with respect to the particle-surface interactions. The latter are governed by micromechanics and are an important aspect for a wide range of industrial applications. Here, a new methodology is developed for understanding the adhesion process and measure the relevant forces, based on the quartz crystal microbalance, QCM. rnThe potential of the QCM technique for studying particle-surface interactions and reflect the adhesion process is evaluated by carrying out experiments with a custom-made setup, consisting of the QCM with a 160 nm thick film of polystyrene (PS) spin-coated onto the quartz and of glass particles, of different diameters (5-20µm), deposited onto the polymer surface. Shifts in the QCM resonance frequency are monitored as a function of the oscillation amplitude. The induced frequency shifts of the 3rd overtone are found to decrease or increase, depending on the particle-surface coupling type and the applied oscillation (frequency and amplitude). For strong coupling the 3rd harmonic decreased, corresponding to an “added mass” on the quartz surface. However, positive frequency shifts are observed in some cases and are attributed to weak-coupling between particle and surface. Higher overtones, i.e. the 5th and 7th, were utilized in order to derive additional information about the interactions taking place. For small particles, the shift for specific overtones can increase after annealing, while for large particle diameters annealing causes a negative frequency shift. The lower overtones correspond to a generally strong-coupling regime with mainly negative frequency shifts observed, while the 7th appears to be sensitive to the contact break-down and the recorded shifts are positive.rnDuring oscillation, the motion of the particles and the induced frequency shift of the QCM are governed by a balance between inertial forces and contact forces. The adherence of the particles can be increased by annealing the PS film at 150°C, which led to the formation of a PS meniscus. For the interpretation, the Hertz, Johnson-Kendall-Roberts, Derjaguin-Müller-Toporov and the Mindlin theory of partial slip are considered. The Mindlin approach is utilized to describe partial slip. When partial slip takes place induced by an oscillating load, a part of the contact ruptures. This results in a decrease of the effective contact stiffness. Additionally, there are long-term memory effects due to the consolidation which along with the QCM vibrations induce a coupling increase. However, the latter can also break the contact, lead to detachment and even surface damage and deformation due to inertia. For strong coupling the particles appear to move with the vibrations and simply act as added effective mass leading to a decrease of the resonance frequency, in agreement with the Sauerbrey equation that is commonly used to calculate the added mass on a QCM). When the system enters the weak-coupling regime the particles are not able to follow the fast movement of the QCM surface. Hence, they effectively act as adding a “spring” with an additional coupling constant and increase the resonance frequency. The frequency shift, however, is not a unique function of the coupling constant. Furthermore, the critical oscillation amplitude is determined, above which particle detach. No movement is detected at much lower amplitudes, while for intermediate values, lateral particle displacement is observed. rnIn order to validate the QCM results and study the particle effects on the surface, atomic force microscopy, AFM, is additionally utilized, to image surfaces and measure surface forces. By studying the surface of the polymer film after excitation and particle removal, AFM imaging helped in detecting three different meniscus types for the contact area: the “full contact”, the “asymmetrical” and a third one including a “homocentric smaller meniscus”. The different meniscus forms result in varying bond intensity between particles and polymer film, which could explain the deviation between number of particles per surface area measured by imaging and the values provided by the QCM - frequency shift analysis. The asymmetric and the homocentric contact types are suggested to be responsible for the positive frequency shifts observed for all three measured overtones, i.e. for the weak-coupling regime, while the “full contact” type resulted in a negative frequency shift, by effectively contributing to the mass increase of the quartz..rnThe interplay between inertia and contact forces for the particle-surface system leads to strong- or weak-coupling, with the particle affecting in three mentioned ways the polymer surface. This is manifested in the frequency shifts of the QCM system harmonics which are used to differentiate between the two interaction types and reflect the overall state of adhesion for particles of different size.rn

The role of macrophages in the clearance of inhaled ultrafine titanium dioxide particles

The role of macrophages in the clearance of particles with diameters less than 100 nm (ultrafine or nanoparticles) is not well established, although these particles deposit highly efficiently in peripheral lungs, where particle phagocytosis by macrophages is the primary clearance mechanism. To investigate the uptake of nanoparticles by lung phagocytes, we analyzed the distribution of titanium dioxide particles of 20 nm count median diameter in macrophages obtained by bronchoalveolar lavage at 1 hour and 24 hours after a 1-hour aerosol inhalation. Differential cell counts revealing greater than 96% macrophages and less than 1% neutrophils and lymphocytes excluded inflammatory cell responses. Employing energy-filtering transmission electron microscopy (EFTEM) for elemental microanalysis, we examined 1,594 macrophage profiles in the 1-hour group (n = 6) and 1,609 in the 24-hour group (n = 6). We found 4 particles in 3 macrophage profiles at 1 hour and 47 particles in 27 macrophage profiles at 24 hours. Model-based data analysis revealed an uptake of 0.06 to 0.12% ultrafine titanium-dioxide particles by lung-surface macrophages within 24 hours. Mean (SD) particle diameters were 31 (8) nm at 1 hour and 34 (10) nm at 24 hours. Particles were localized adjacent (within 13-83 nm) to the membrane in vesicles with mean (SD) diameters of 592 (375) nm at 1 hour and 414 (309) nm at 24 hours, containing other material like surfactant. Additional screening of macrophage profiles by conventional TEM revealed no evidence for agglomerated nanoparticles. These results give evidence for a sporadic and rather unspecific uptake of TiO(2)-nanoparticles by lung-surface macrophages within 24 hours after their deposition, and hence for an insufficient role of the key clearance mechanism in peripheral lungs.