Radio frequency plasma-induced hydrogen bonding on kaolinite

The radio frequency (RF) plasma-modified surfaces of kaolinite were investigated by diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) and deuteration techniques to determine the nature of RF plasma-induced surface functional groups, the altered sites in the lattice, and interaction mechanism between RF plasma and the surface of the kaolinite. It has been concluded that the RF plasma-induced infrared (IR) vibration absorption bands at 2805, 3010, and 3100 cm(-1) are attributable to the stretching vibration of hydrogen-bonded hydroxyl groups, and the band at 1407 cm(-1) is attributable to the bending vibration of (HO-)Al-O or (HO-)Si-O groupings with hydrogen-bonded hydroxyl groups. Structural alteration occurred on both the surface and subsurface region of the kaolinite during RF plasma treatment. Further structural alteration or adjustment was also observed on well-modified and well-deuterated kaolinite. There are two types of OD bands visible in the DRIFT spectra of this kaolinite, one type which decreased rapidly as a function of time in moist air, and the other which remained unchanged during the measurement. Furthermore, the appearance of broad IR bands at 3500-3100 cm(-1) as a result of deuteration is evidence of structural disturbance by RF plasma treatment lattice deuteration. An RF plasma-induced hydrogen bonding model on the surface of the kaolinite is proposed.

Contextual binding of p120ctn to E-cadherin at the basolateral plasma membrane in polarized epithelia

E-cadherin-catenin complexes mediate cell-cell adhesion on the basolateral membrane of epithelial cells. The cytoplasmic tail of E-cadherin supports multiple protein interactions, including binding of beta-catenin at the C terminus and of p120(ctn) to the juxtamembrane domain. The temporal assembly and polarized trafficking of the complex or its individual components to the basolateral membrane are not fully understood. In Madin-Darby canine kidney cells at steady state and after treatment with cycloheximide or temperature blocks, E-cadherin and beta-catenin localized to the Golgi complex, but p120ctn was found only at the basolateral plasma membrane. We previously identified a dileucine sorting motif (Leu(586)-Leu(587), termed S1) in the juxtamembrane domain of E-cadherin and now show that it is required to target full-length E-cadherin to the basolateral membrane. Removal of S1 resulted in missorting of E-cadherin mutants (EcadDeltaS1) to the apical membrane; beta-catenin was simultaneously missorted and appeared at the apical membrane. p120(ctn) was not mistargeted with EcadDeltaS1, but could be recruited to the E-cadherin-catenin complex only at the basolateral membrane. These findings help define the temporal assembly and sorting of the E-cadherin-catenin complex and show that membrane recruitment of p120(ctn) in polarized cells is contextual and confined to the basolateral membrane.

Transdermal penetration of vasoconstrictors - Present understanding and assessment of the human epidermal flux and retention of free bases and ion-pairs

Purpose. As reductions in dermal clearance increase the residence time of solutes in the skin and underlying tissues we compared the topical penetration of potentially useful vasoconstrictors (VCs) through human epidermis as both free bases and ion-pairs with salicylic acid (SA). Methods. We determined the in vitro epidermal flux of ephedrine, naphazoline, oxymetazoline, phenylephrine, and xylometazoline applied as saturated solutions in propylene glycol: water (1: 1) and of ephedrine, naphazoline and tetrahydrozoline as 10% solutions of 1: 1 molar ratio ion-pairs with SA in liquid paraffin. Results. As free bases, ephedrine had the highest maximal flux, Jmax = 77.4 +/- 11.7 mug/cm(2)/h, being 4-fold higher than tetrahydrozoline and xylometazoline, 6-fold higher than phenylephrine, 10-fold higher than naphazoline and 100-fold higher than oxymetazoline. Stepwise regression of solute physicochemical properties identified melting point as the most significant predictor of flux. As ion-pairs with SA, ephedrine and naphazoline had similar fluxes (11.5 +/- 2.3 and 12.0 +/- 1.6 mug/cm(2)/h respectively), whereas tetrahydrozoline was approximately 3-fold slower. Corresponding fluxes of SA from the ion-pairs were 18.6 +/- 0.6, 7.8 +/- 0.8 and 1.1 +/- 0.1 respectively. Transdermal transport of VC's is discussed. Conclusions. Epidermal retention of VCs and SA did not correspond to their molar ratio on application and confirmed that following partitioning into the stratum corneum, ion-pairs separate and further penetration is governed by individual solute characteristics.

Water table waves in an unconfined aquifer: Experiments and modeling

[1] Comprehensive measurements are presented of the piezometric head in an unconfined aquifer during steady, simple harmonic oscillations driven by a hydrostatic clear water reservoir through a vertical interface. The results are analyzed and used to test existing hydrostatic and nonhydrostatic, small-amplitude theories along with capillary fringe effects. As expected, the amplitude of the water table wave decays exponentially. However, the decay rates and phase lags indicate the influence of both vertical flow and capillary effects. The capillary effects are reconciled with observations of water table oscillations in a sand column with the same sand. The effects of vertical flows and the corresponding nonhydrostatic pressure are reasonably well described by small-amplitude theory for water table waves in finite depth aquifers. That includes the oscillation amplitudes being greater at the bottom than at the top and the phase lead of the bottom compared with the top. The main problems with respect to interpreting the measurements through existing theory relate to the complicated boundary condition at the interface between the driving head reservoir and the aquifer. That is, the small-amplitude, finite depth expansion solution, which matches a hydrostatic boundary condition between the bottom and the mean driving head level, is unrealistic with respect to the pressure variation above this level. Hence it cannot describe the finer details of the multiple mode behavior close to the driving head boundary. The mean water table height initially increases with distance from the forcing boundary but then decreases again, and its asymptotic value is considerably smaller than that previously predicted for finite depth aquifers without capillary effects. Just as the mean water table over-height is smaller than predicted by capillarity-free shallow aquifer models, so is the amplitude of the second harmonic. In fact, there is no indication of extra second harmonics ( in addition to that contained in the driving head) being generated at the interface or in the interior.

Plasma zinc and immune markers in runners in response to a moderate increase in training volume

Changes in plasma zinc concentration and markers of immune function were examined in a group of 10 male runners (n = 10) following a moderate increase in training over four weeks. Seven sedentary males acted as controls. Fasting blood samples were taken at rest, before (T0) and after T4) four weeks of increased (+ 16 %) training and after two weeks of reduced (- 31 %) training (W. Blood was analysed for plasma zinc concentration, differential leucocyte counts, lymphocyte subpopulations and lymphocyte proliferation using incorporation of H-3-thymidine. The runners increased their training volume by 16 % over the four weeks. When compared with the nonathletes, the runners had lower concentrations of plasma zinc (p = 0.012), CD3(+) (p = 0.042) and CD19(+) lymphocytes (p = 0.010) over the four weeks. Lymphocyte proliferation in response to Concanavalin A stimulation was greater in the runners (p = 0.0090). Plasma zinc concentration and immune markers remained constant during the study. Plasma zinc concentration correlated with total leucocyte counts in the athletes at T6 (r = -0.72, p < 0.05) and with Pokeweed mitogen stimulation in the nonathletes at T6 (r = -0.92, p < 0.05). Therefore, athletes are unlikely to benefit from zinc supplementation during periods of moderately increased training volume.

Selective entrainment of sediment graded by size and density under waves

The influence of near-bed sorting processes on heavy mineral content in suspension is discussed. Sediment concentrations above a rippled bed of mixed quartz and heavy mineral sand were measured under regular nonbreaking waves in the laboratory. Using the traditional gradient diffusion process, settling velocity would be expected to strongly affect sediment distribution. This was not observed during present trials. In fact, the vertical gradients of time-averaged suspension concentrations were found to be similar for the light and heavy minerals, despite their different settling velocities. This behavior implies a convective rather than diffusive distribution mechanism. Between the nonmoving bed and the lowest suspension sampling point, fight and heavy mineral concentration differs by two orders of magnitude. This discrimination against the heavy minerals in the pickup process is due largely to selective entrainment at the ripple face. Bed-form dynamics and the nature of quartz suspension profiles are found to be little affected by the trialed proportion of overall heavy minerals in the bed (3.8-22.1%).

Gravitational waves : a 100-year tool applied to the dark energy problem

Recent observations from type Ia Supernovae and from cosmic microwave background (CMB) anisotropies have revealed that most of the matter of the Universe interacts in a repulsive manner, composing the so-called dark energy constituent of the Universe. Determining the properties of dark energy is one of the most important tasks of modern cosmology and this is the main motivation for this work. The analysis of cosmic gravitational waves (GW) represents, besides the CMB temperature and polarization anisotropies, an additional approach in the determination of parameters that may constrain the dark energy models and their consistence. In recent work, a generalized Chaplygin gas model was considered in a flat universe and the corresponding spectrum of gravitational waves was obtained. In the present work we have added a massless gas component to that model and the new spectrum has been compared to the previous one. The Chaplygin gas is also used to simulate a L-CDM model by means of a particular combination of parameters so that the Chaplygin gas and the L-CDM models can be easily distinguished in the theoretical scenarios here established. We find that the models are strongly degenerated in the range of frequencies studied. This degeneracy is in part expected since the models must converge to each other when some particular combinations of parameters are considered.

Effect of fiber orientation in gelled poly (vinylience fluoride) electrospun membranes for Li-ion battery applications

Battery separators based on electrospun membranes of poly(vinylidene fluoride) (PVDF) have been prepared in order to study the effect of fiber alignment on the performance and characteristics of the membrane. The prepared membranes show an average fiber diameter of ~272 nm and a degree of porosity of ~87 %. The gel polymer electrolytes are prepared by soaking the membranes in the electrolyte solution. The alignment of the fibers improves the mechanical properties for the electrospun membranes. Further, the microstructure of the membrane also plays an important role in the ionic conductivity, being higher for the random electrospun membrane due to the lower tortuosity value. Independently of the microstructure, both membranes show good electrochemical stability up to 5.0 V versus Li/Li+. These results show that electrospun membranes based on PVDF are appropriate for battery separators in lithium-ion battery applications, the random membranes showing a better overall performance.

Implementação e validação do método de determinação de metais e fósforo por ICP-OES (inductively coupled plasma-optical emission spectometry) em biodiesel

O objectivo do presente trabalho foi desenvolver, implementar e validar métodos de determinação de teor de cálcio (Ca), magnésio (Mg), sódio (Na), potássio (K) e fósforo (P) em biodiesel, por ICP-OES. Este método permitiu efectuar o controlo de qualidade do biodiesel, com a vantagem de proporcionar uma análise multi-elementar, reflectindo-se numa diminuição do tempo de análise. Uma vez que o biodiesel é uma das principais fontes de energia renovável e alternativa ao diesel convencional, este tipo de análises revela-se extremamente útil para a sua caracterização. De acordo com a análise quantitativa e qualitativa e após a validação dos respectivos ensaios, apresentam-se, na Tabela 1 as condições optimizadas para cada elemento em estudo. As condições de trabalho do ICP-OES foram escolhidas tendo em conta as características do elemento em estudo, o tipo de equipamento utilizado para a sua análise, e de modo a obter a melhor razão sinal/intensidade de fundo. Para a validação dos ensaios foram efectuados ensaios de recuperação, determinados limites de detecção e quantificação, ensaios de repetibilidade e reprodutibilidade, e verificação das curvas de calibração. Na tabela 2 apresentam-se os comprimentos de onda escolhidos (livres de interferências) e respectivos limites de detecção e quantificação dos elementos analisados por ICP-OES, na posição radial e radial atenuado.

Development of a biosensor for urea assay based on amidase inhibition, using an ion-selective electrode

A biosensor for urea has been developed based on the observation that urea is a powerful active-site inhibitor of amidase, which catalyzes the hydrolysis of amides such as acetamide to produce ammonia and the corresponding organic acid. Cell-free extract from Pseudomonas aeruginosa was the source of amidase (acylamide hydrolase, EC 3.5.1.4) which was immobilized on a polyethersulfone membrane in the presence of glutaraldehyde; anion-selective electrode for ammonium ions was used for biosensor development. Analysis of variance was used for optimization of the biosensorresponse and showed that 30 mu L of cell-free extract containing 7.47 mg protein mL(-1), 2 mu L of glutaraldehyde (5%, v/v) and 10 mu L of gelatin (15%, w/v) exhibited the highest response. Optimization of other parameters showed that pH 7.2 and 30 min incubation time were optimum for incubation ofmembranes in urea. The biosensor exhibited a linear response in the range of 4.0-10.0 mu M urea, a detection limit of 2.0 mu M for urea, a response timeof 20 s, a sensitivity of 58.245 % per mu M urea and a storage stability of over 4 months. It was successfully used for quantification of urea in samples such as wine and milk; recovery experiments were carried out which revealed an average substrate recovery of 94.9%. The urea analogs hydroxyurea, methylurea and thiourea inhibited amidase activity by about 90%, 10% and 0%, respectively, compared with urea inhibition.

Mass spectrometry improvement on an high current ion implanter

The development of accurate mass spectrometry, enabling the identification of all the ions extracted from the ion source in a high current implanter is described. The spectrometry system uses two signals (x-y graphic), one proportional to the magnetic field (x-axes), taken from the high-voltage potential with an optic fiber system, and the other proportional to the beam current intensity (y-axes), taken from a beam-stop. The ion beam mass register in a mass spectrum of all the elements magnetically analyzed with the same radius and defined by a pair of analyzing slits as a function of their beam intensity is presented. The developed system uses a PC to control the displaying of the extracted beam mass spectrum, and also recording of all data acquired for posterior analysis. The operator uses a LabView code that enables the interfacing between an I/O board and the ion implanter. The experimental results from an ion implantation experiment are shown. (C) 2011 Elsevier B.V. All rights reserved.

Avaliação da integridade estrutural de uma prótese cimentada por emissão acústica

Mestrado em Engenharia Electrotécnica e de Computadores