Enhancement of hematoporphyrin IX potential for photodynamic therapy by entrapment in silica nanospheres

The entrapment of hematoporphyrin IX (Hp IX) in silica by means of a microemulsion resulted in silica spheres of 33 +/- 6 nm. The small size, narrow size distribution and lack of aggregation maintain Hp IX silica nanospheres stable in aqueous solutions for long periods and permit a detailed study of the entrapped drug by different techniques. Hp IX entrapped in the silica matrix is accessed by oxygen and upon irradiation generates singlet oxygen which diffuses very efficiently to the outside solution. The Hp IX entrapped in the silica matrix is also reached by iron(II) ions, which causes quenching of the porphyrin fluorescence emission. The silica matrix also provides extra protection to the photosensitizer against interaction with BSA and ascorbic acid, which are known to cause suppression of singlet oxygen generation by the Hp IX free in solution. Therefore, the incorporation of Hp IX molecules into silica nanospheres increased the potential of the photosensitizer to perform photodynamic therapy.

Characterization of dynamic solid phase DNA extraction from blood with magnetically controlled silica beads

A novel solid phase extraction technique is described where DNA is bound and eluted from magnetic silica beads in a manner where efficiency is dependent on the magnetic manipulation of the beads and not on the flow of solution through a packed bed. The utility of this technique in the isolation of reasonably pure, PCR-amplifiable DNA from complex samples is shown by isolating DNA from whole human blood, and subsequently amplifying a fragment of the beta-globin gene. By effectively controlling the movement of the solid phase in the presence of a static sample, the issues associated with reproducibly packing a solid phase in a microchannel and maintaining consistent flow rates are eliminated. The technique described here is rapid, simple, and efficient, allowing for recovery of more than 60% of DNA from 0.6 mu L of blood at a concentration which is suitable for PCR amplification. In addition, the technique presented here requires inexpensive, common laboratory equipment, making it easily adopted for both clinical point-of-care applications and on-site forensic sample analysis.

Abundance of sedentary consumers and sessile organisms along the wave exposure gradient of subtropical rocky shores of the south-west Atlantic

Sedentary consumers play an important role on populations of prey and, hence, their patterns of abundance, distribution and coexistence on shores are important to evaluate their potential influence on ecosystem dynamics. Here, we aimed to describe their spatio-temporal distribution and abundance in relation to wave exposure in the intertidal rocky shores of the south-west Atlantic to provide a basis for further understanding of ecological processes in this system. The abundance and composition of the functional groups of sessile organisms and sedentary consumers were taken by sampling the intertidal of sheltered and moderately exposed shores during a period of one year. The sublittoral fringe of sheltered areas was dominated by macroalgae, while the low midlittoral was dominated by bare rock and barnacles. In contrast, filter-feeding animals prevailed at exposed shores, probably explaining the higher abundance of the predator Stramonita haemastoma at these locations. Limpets were more abundant at the midlittoral zone of all shores while sea urchins were exclusively found at the sublittoral fringe of moderately exposed shores, therefore, adding grazing pressure on these areas. The results showed patterns of coexistence, distribution and abundance of those organisms in this subtropical area, presumably as a result of wave action, competition and prey availability. It also brought insights on the influence of top-down and bottom-up processes in this area.

Stability analysis of core-annular flow and neutral stability wave number

A general transition criterion is proposed in order to locate the core-annular flow pattern in horizontal and vertical oil-water flows. It is based on a rigorous one-dimensional two-fluid model of liquid-liquid two-phase flow and considers the existence of critical interfacial wave numbers related to a non-negligible interfacial tension term to which the linear stability theory still applies. The viscous laminar-laminar flow problem is fully resolved and turbulence effects on the stability are analyzed through experimentally obtained shape factors. The proposed general transition criterion includes in its formulation the inviscid Kelvin-Helmholtz`s discriminator. If a theoretical maximum wavelength is considered as a necessary condition for stability, a stability criterion in terms of the Eotvos number is achieved. Effects of interfacial tension, viscosity ratio, density difference, and shape factors on the stability of core-annular flow are analyzed in detail. The more complete modeling allowed for the analysis of the neutral-stability wave number and the results strongly suggest that the interfacial tension term plays an indispensable role in the correct prediction of the stable region of core-annular flow pattern. The incorporation of a theoretical minimum wavelength into the transition model produced significantly better results. The criterion predictions were compared with recent data from the literature and the agreement is encouraging. (C) 2007 American Institute of Chemical Engineers.

Bidimensional codes recorded on an oxide glass surface using a continuous wave CO(2) laser

Surface heat treatment in glasses and ceramics, using CO(2) lasers, has attracted the attention of several researchers around the world due to its impact in technological applications, such as lab-on-a-chip devices, diffraction gratings and microlenses. Microlens fabrication on a glass surface has been studied mainly due to its importance in optical devices (fiber coupling, CCD signal enhancement, etc). The goal of this work is to present a systematic study of the conditions for microlens fabrications, along with the viability of using microlens arrays, recorded on the glass surface, as bidimensional codes for product identification. This would allow the production of codes without any residues (like the fine powder generated by laser ablation) and resistance to an aggressive environment, such as sterilization processes. The microlens arrays were fabricated using a continuous wave CO(2) laser, focused on the surface of flat commercial soda-lime silicate glass substrates. The fabrication conditions were studied based on laser power, heating time and microlens profiles. A He-Ne laser was used as a light source in a qualitative experiment to test the viability of using the microlenses as bidimensional codes.

CONCENTRATION FIELDS NEAR AIR-WATER INTERFACES DURING INTERFACIAL MASS TRANSPORT: OXYGEN TRANSPORT AND RANDOM SQUARE WAVE ANALYSIS

Mass transfer across a gas-liquid interface was studied theoretically and experimentally, using transfer of oxygen into water as the gas-liquid system. The experimental results support the conclusions of a theoretical description of the concentration field that uses random square waves approximations. The effect of diffusion over the concentration records was quantified. It is shown that the peak of the normalized rills concentration fluctuation profiles must be lower than 0.5, and that the position of the peak of the rms value is an adequate measure of the thickness of the diffusive layer. The position of the peak is the boundary between the regions more subject to molecular diffusion or to turbulent transport of dissolved mass.

Experimental study of a Tollmien-Schlichting wave interacting with a shallow 3D roughness element

The paper is devoted to an experimental study of the effect of a shallow 3D roughness element on the evolution of a 2D Tollmien-Schlichting wave in a Blasius boundary layer. The experiments were carried out under controlled disturbance conditions on an airfoil section which could provide a long run with zero pressure gradient flow. A pneumatically driven slit source was used to introduce the Tollmien-Schilichting wave upstream of the lower branch of the neutral stability curve. A few wavelengths downstream, the T-S wave interacts with a cylindrical roughness element. The height of the roughness was slowly oscillating in time, which allows a continuous measurement of the T-S wave response downstream the roughness. The oscillation frequency was approximately 1500 times lower than the frequency of the studied Tollmien-Schlichting wave and therefore, behaved as a steady roughness with respect to the T-S wave. Hot wire anemometry was used to measure wall normal profiles and spanwise scans close to the maximum of the eigenfunction of the T-S wave. The oscillation of the roughness and the synchronization of all-equipments permitted the use of ensemble average techniques. Two different amplitudes of T-S waves with a non-dimensional frequency of F120E-06 were studied. They show a strong amplification of the disturbances in a small spanwise wave number range. The analysis of the wall normal T-S profiles suggests the growth of oblique modes.

Separation of silica from bauxite via froth flotation

This paper reports an innovative development: concentrating gibbsite via reverse froth flotation in order to obtain a metallurgical-grade bauxite concentrate. Tailings from an industrial plant have undergone attrition scrubbing and desliming; the quartz silica contained in the tailings has undergone flotation. Starch was used as a depressant, and ether-amine as the cationic collector. Optimum pH is around 10.0. In pilot plant scale, a metallurgical-grade concentrate was obtained by assaying 42.3% available alumina with an alumina/insoluble silica mass ratio of 11.1. It contained the gibbsite and the iron and titanium bearing minerals. The concentrate was further upgraded by magnetic separation, leading to 54.0% available alumina, with an alumina/insoluble silica mass ratio of 12.6 at an overall available alumina recovery of 69.3% in the final concentrate (non-magnetic product). (C) 2008 Elsevier Ltd. All rights reserved.

Ultrasonic Viscosity Measurement Using the Shear-Wave Reflection Coefficient with a Novel Signal Processing Technique

Real-time viscosity measurement remains a necessity for highly automated industry. To resolve this problem, many studies have been carried out using an ultrasonic shear wave reflectance method. This method is based on the determination of the complex reflection coefficient`s magnitude and phase at the solid-liquid interface. Although magnitude is a stable quantity and its measurement is relatively simple and precise, phase measurement is a difficult task because of strong temperature dependence. A simplified method that uses only the magnitude of the reflection coefficient and that is valid under the Newtonian regimen has been proposed by some authors, but the obtained viscosity values do not match conventional viscometry measurements. In this work, a mode conversion measurement cell was used to measure glycerin viscosity as a function of temperature (15 to 25 degrees C) and corn syrup-water mixtures as a function of concentration (70 to 100 wt% of corn syrup). Tests were carried out at 1 MHz. A novel signal processing technique that calculates the reflection coefficient magnitude in a frequency band, instead of a single frequency, was studied. The effects of the bandwidth on magnitude and viscosity were analyzed and the results were compared with the values predicted by the Newtonian liquid model. The frequency band technique improved the magnitude results. The obtained viscosity values came close to those measured by the rotational viscometer with percentage errors up to 14%, whereas errors up to 96% were found for the single frequency method.

Comparison between DC(+) and Square Wave AC SAW Current Outputs to Weld AISI 304 for Low-Temperature Applications

Welded equipment for cryogenic applications is utilized in chemical, petrochemical, and metallurgical industries. One material suitable for cryogenic application is austenitic stainless steel, which usually doesn`t present ductile/brittle transition temperature, except in the weld metal, where the presence of ferrite and micro inclusions can promote a brittle failure, either by ferrite cleavage or dimple nucleation and growth, respectively. A 25-mm- (1-in.-) thick AISI 304 stainless steel base metal was welded with the SAW process using a 308L solid wire and two kinds of fluxes and constant voltage power sources with two types of electrical outputs: direct current electrode positive and balanced square wave alternating current. The welded joints were analyzed by chemical composition, microstructure characterization, room temperature mechanical properties, and CVN impact test at -100 degrees C (-73 degrees F). Results showed that an increase of chromium and nickel content was observed in all weld beads compared to base metal. The chromium and nickel equivalents ratio for the weld beads were always higher for welding with square wave AC for the two types of fluxes than for direct current. The modification in the Cr(eq)/Ni(eq) ratio changes the delta ferrite morphology and, consequently, modifies the weld bead toughness at lower temperatures. The oxygen content can also affect the toughness in the weld bead. The highest absorbed energy in a CVN impact test was obtained for the welding condition with square wave AC electrical output and neutral flux, followed by DC(+) electrical output and neutral flux, and square wave AC electrical output and alloyed flux.

Estimating wave spectra from the motions of moored vessels: Experimental validation

The practicability of estimating directional wave spectra based on a vessel`s 1st order response has been recently addressed by several researchers. Different alternatives regarding statistical inference methods and possible drawbacks that could arise from their application have been extensively discussed, with an apparent preference for estimations based on Bayesian inference algorithms. Most of the results on this matter, however, rely exclusively on numerical simulations or at best on few and sparse full-scale measurements, comprising a questionable basis for validation purposes. This paper discusses several issues that have recently been debated regarding the advantages of Bayesian inference and different alternatives for its implementation. Among those are the definition of the best set of input motions, the number of parameters required for guaranteeing smoothness of the spectrum in frequency and direction and how to determine their optimum values. These subjects are addressed in the light of an extensive experimental campaign performed with a small-scale model of an FPSO platform (VLCC hull), which was conducted in an ocean basin in Brazil. Tests involved long and short crested seas with variable levels of directional spreading and also bimodal conditions. The calibration spectra measured in the tank by means of an array of wave probes configured the paradigm for estimations. Results showed that a wide range of sea conditions could be estimated with good precision, even those with somewhat low peak periods. Some possible drawbacks that have been pointed out in previous works concerning the viability of employing large vessels for such a task are then refuted. Also, it is shown that a second parameter for smoothing the spectrum in frequency may indeed increase the accuracy in some situations, although the criterion usually proposed for estimating the optimum values (ABIC) demands large computational effort and does not seem adequate for practical on-board systems, which require expeditious estimations. (C) 2009 Elsevier Ltd. All rights reserved.

Directional Wave Spectrum Estimation Based on Vessel`s 1st-order Motions: Field Results

In this paper, 2 different approaches for estimating the directional wave spectrum based on a vessel`s 1st-order motions are discussed, and their predictions are compared to those provided by a wave buoy. The real-scale data were obtained in an extensive monitoring campaign based on an FPSO unit operating at Campos Basin, Brazil. Data included vessel motions, heading and tank loadings. Wave field information was obtained by means of a heave-pitch-roll buoy installed in the vicinity of the unit. `two of the methods most widely used for this kind of analysis are considered, one based on Bayesian statistical inference, the other consisting of a parametrical representation of the wave spectrum. The performance of both methods is compared, and their sensitivity to input parameters is discussed. This analysis complements a set of previous validations based on numerical and towing-tank results and allows for a preliminary evaluation of reliability when applying the methodology at full scale.

Corrosion behavior of carbon steel protected with single and bi-layer of silane films filled with silica nanoparticles

The electrochemical behaviour of carbon steel coated with bis-[trimethoxysilylpropyl]amine (BTSPA) filled with silica nanoparticles in naturally aerated 0.1 mol L-1 NaCl solutions was evaluated. The coating was prepared by adding different concentrations of silica nanoparticles (100, 200, 300, 400 and 500 ppm) to the hydrolysis solution and then a second layer without silica nanoparticles was applied. The electrochemical behavior of the coated steel was evaluated by means of open-circuit potential (E-OC), electrochemical impedance spectroscopy (EIS) and polarization curves. Surface characterization was made by atomic force microscopy (AFM), and its hydrophobicity assessed by contact angle measurements. EIS diagrams have shown an improvement of the barrier properties of the silane layer with the silica addition, which was further improved on the bi-layer system. However, a dependence on the filler concentration was verified, and the best electrochemical response was obtained for samples modified with 300 ppm of silica nanoparticles. AFM images have shown a homogeneous distribution of the silica nanoparticles on the sample surface; however particles agglomeration was detected, which degraded the corrosion protection performance. The results were explained on the basis of the improvement of the barrier properties of the coating due to the filler addition and on the onset of defective regions on the more heavily filled coatings allowing easier electrolyte penetration. (C) 2007 Elsevier B.V. All rights reserved.

Effect of Charge Asymmetry on Adsorption and Phase Separation of Polyampholytes on Silica and Cellulose Surfaces

The relation between the properties of polyampholytes in aqueous solution and their adsorption behaviors on silica and cellulose surfaces was investigated. Four polyampholytes carrying different charge densities but with the same nominal ratio of positive to negative segments and two structurally similar polyelectrolytes (a polyacid and a polybase) were investigated by using quartz crystal microgravimetry using silica-coated and cellulose-coated quartz resonators. Time-resolved mass and rigidity (or viscoelasticity) of the adsorbed layer was determined from the shifts in frequency (Delta f) and energy dissipation (Delta D) of the respective resonator. Therefore, elucidation of the dynamics and extent of adsorption, as well as the conformational changes of the adsorbed macromolecules, were possible. The charge properties of the solid Surface played a crucial role in the adsorption of the studied polyampholytes, which was explained by the capability of the surface to polarize the polyampholyte at the interface. Under the same experimental conditions, the polyampholytes had a higher nominal charge density phase-separated near the interface, producing a soft, dissipative, and loosely bound layer. In the case of cellulose substrates, where adsorption was limited, electrostatic and polarization effects were concluded to be less significant.

Biogenic modified silica as a sorbent of cadmium ions: Preparation and characterization

This work describes the preparation and characterization of biogenic modified silica from rice hull ash and its use as a sorbent of cadmium ions. Thus, an agro-industrial residue has been used to produce a new adsorbent product which is able to remove toxic elements. Mesoporous biogenic silica was obtained by alkaline extraction of sodium silicate by hydrolysis with the sol-gel process, and it was modified with salen using 1,2-dichloroethane as a spacer. The surface area of the silica was measured by nitrogen adsorption/desorption analysis. Surface modification was measured by Fourier transform infrared spectroscopy. The degree of functionalization was obtained by elemental analysis. This work showed that biogenic modified silica can be produced in aqueous media from rice hull ash using a simple method, providing an alternative method for adsorbent preparation. Thermogravimetric analysis showed that the salen-modified silica is stable up to 209 C. The modified silica displays appropriate structural characteristics for an adsorbent. The cylindrical pores, open at both ends, allow free diffusion of cadmium ions to the adsorption sites on the silica surface. The surface modification increases cadmium adsorption on the silica surface 100-fold. The salen-modified silica showed specific adsorption for Cd2+ of 44.52 mg/g SiO2 at cadmium concentration of 100 mg/l.