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Biomedical subjects

Franz Grieser

Publications and source records attributed to Franz Grieser.

At least 19 recordsLinked to original sources

Effect of alcohols on the initial growth of multibubble sonoluminescence.

The effect of alcohols on the initial growth of the multibubble sonoluminescence (MBSL) intensity in aqueous solutions has been investigated. With increasing concentrations of the alcohols, the number of pulses required to grow the MBSL intensity to a steady state (N(crit)) increases (relative to that of water) initially to a maximum for all the alcohols used in this study, followed by a decrease for methanol and ethanol. The cause of the initial increase in N(crit) is attributed to the inhibition of bubble coalescence in the system. This inhibition in bubble coalescence results in a population of bubbles with a smaller size range and thus a larger number of pulses is required to grow the bubbles to their sonoluminescing size range. It is suggested that the decrease in the N(crit) at higher alcohol concentrations may be caused by an increase in the bubble growth by rectified diffusion.

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Dynamic forces between two deformable oil droplets in water.

The understanding of static interactions in colloidal suspensions is well established, whereas dynamic interactions more relevant to biological and other suspended soft-matter systems are less well understood. We present the direct force measurement and quantitative theoretical description for dynamic forces for liquid droplets in another immiscible fluid. Analysis of this system demonstrates the strong link between interfacial deformation, static surface forces, and hydrodynamic drainage, which govern dynamic droplet-droplet interactions over the length scale of nanometers and over the time scales of Brownian collisions. The results and analysis have direct bearing on the control and manipulation of suspended droplets in soft-matter systems ranging from the emulsions in shampoo to cellular interactions.

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Determination of temperatures within acoustically generated bubbles in aqueous solutions at different ultrasound frequencies.

Mean acoustic bubble temperatures have been measured using a methyl radical recombination (MRR) method, at three ultrasound frequencies (20, 355, and 1056 kHz) in aqueous tert-butyl alcohol solutions (0-0.5 M). The method is based on yield measurements of some of the hydrocarbon products formed from the recombination of methyl radicals that are thermally generated within collapsing bubbles containing tert-butyl alcohol vapor. The mean bubble temperatures were found to decrease substantially with increasing tert-butyl alcohol concentration at 355 and 1056 kHz but only to a small extent at 20 kHz. Extrapolating the mean temperatures measured to zero concentration of tert-butyl alcohol, at a bulk solution temperature of 20 degrees C, gave the order 355 kHz (4300 +/- 200 K) > 1056 kHz (3700 +/- 200 K) > 20 kHz (3400 +/- 200 K). It is also concluded that the temperature derived from the MRR method is a useful diagnostic parameter for sensing the thermal conditions within an active acoustic bubble. However, attention must be given to the fact that the temperature derived from the MRR method is not theoretically well defined.

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Limitations of the methyl radical recombination method for acoustic cavitation bubble temperature measurements in aqueous solutions.

The methyl radical recombination (MRR) method has been used for the measurement of cavitation bubble temperatures in aqueous solutions containing a select group of aromatic hydrocarbons as the source for the methyl radicals. The aromatic solutes used were phenol, aniline, m-cresol, and o-toluidine. The maximum bubble core temperatures determined using aniline and phenol were observed to be comparatively high with respect to other reported literature methods and also where the methyl radicals were produced from the cavitation thermolysis of simple aliphatic alcohols. It is concluded that the MRR method cannot be used with organic compounds that do not predominantly produce methyl radicals on the thermal decomposition of the hydrocarbon solutes within the hot core of a collapsing bubble.

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Sonochemically prepared platinum-ruthenium bimetallic nanoparticles.

Colloidal bimetallic nanoparticles of Pt-Ru have been synthesized by sonochemical reduction of Pt(II) and Ru(III) in aqueous solutions. Transmission electron microscope (TEM) images indicate that sequential reduction of the Pt(II) followed by the Ru(III) produces particles with a core shell (Pt@Ru) morphology. In the presence of sodium dodecyl sulfate, SDS, as a stabilizer, the particles have diameters between 5 and 10 nm. When polyvinyl-2-pyrrolidone, PVP, is used as the stabilizer, the rate of reduction is much faster, giving ultrasmall bimetallic particles of approximately 5 nm diameter.

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Effect of surfactants on the kinetics of nickel(II) extraction by 2-hydroxy-5-nonylacetophenone oxime (LIX 84) in an n-heptane/water system.

The initial reaction rates of the extraction of nickel(II) by 2-hydroxy-5-nonylacetophenone oxime (HNAPO) in a two-phase oil/water system was measured using a total internal reflectance static transfer cell. A two-step reaction mechanism between nickel(II) and HNAPO was found to satisfactorily explain the observed initial reaction rate (R(int)). The addition of neutral surfactants, nonionic octaethylene glycol mono-n-dodecyl ether and zwitterionic n-dodecyldimethyl-3-ammonio-1-propanesulfonate, decreased R(int), which could be accounted for with a competitive surface adsorption model. The presence of the anionic surfactant sodium dodecyl sulfate accelerated and then decelerated R(int), while the cationic surfactant dodecyltrimethylammonium chloride caused a decrease. The effects of these charged surfactants were accounted for using a combination of a competitive surface adsorption model and the Boltzmann distribution of charged species.

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Sonochemical synthesis of gold nanoparticles: effects of ultrasound frequency.

The rate of sonochemical reduction of Au(III) to produce Au nanoparticles in aqueous solutions containing 1-propanol has been found to be strongly dependent upon the ultrasound frequency. The size and distribution of the Au nanoparticles produced can also be correlated with the rate of Au(III) reduction, which in turn is influenced by the applied frequency. Our results suggest that the rate of Au(III) reduction as well as the size distribution of Au particles are governed by the chemical effects of cavitation and are not significantly affected by the physical effects accompanying ultrasound-induced cavitation.

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The influence of acoustic power on multibubble sonoluminescence in aqueous solution containing organic solutes.

The effect of varying the applied acoustic power on the extent to which the addition of water-soluble solutes affect the intensity of aqueous multibubble sonoluminescence (MBSL) has been investigated. Under most of the experimental conditions used, the addition of aliphatic alcohols to aqueous solutions was found to suppress the MBSL intensity, although an enhancement of the MBSL intensity was also observed under certain conditions. In contrast, the presence of an anionic surfactant sodium dodecyl sulfate (SDS) in aqueous solutions generally enhanced the observed MBSL intensity. For a series of aliphatic alcohols and SDS, a strong dependence of the MBSL intensity on the applied acoustic power (in the range of 0.78-1.61 W/cm(2)) at 358 kHz was observed. The relative SL quenching was significantly higher at higher acoustic powers for the alcohol solutions, whereas the relative SL enhancement was lower at higher acoustic powers in SDS solutions. These observations have been interpreted in terms of a combination of material evaporation into the bubble, rectified diffusion, bubble clustering and bubble-bubble coalescence.

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Proton transfer between organic acids and bases at the acoustic bubble-aqueous solution interface.

The multibubble sonoluminescence (MBSL) emission intensity from aqueous solutions containing simple aliphatic organic acids (RCOOH) and bases (RNH2) and mixtures of the two types of solutes has been examined as a function of pH. In solutions containing either an organic acid or base, under pH conditions where the solutes are predominately in their ionized form (i.e., RCOO- and RNH3+), the MBSL intensity is identical with that obtained in pure water. Alternatively, under pH conditions where the solutes are in their un-ionized form the MBSL intensity is suppressed. However, in solute mixtures of RCOO- and RNH3+ in the pH range of 7 to 9, the MBSL intensity was significantly suppressed relative to that from water. To explain the results of the mixed solute system it has been postulated that when the bubble/solution interface experiences the extreme temperature conditions that accompany bubble collapse, proton transfer occurs between acid-base ion-pair complexes, [RCOO-...RNH3+], adsorbed at the bubble/solution interface. The neutral forms of the solutes then evaporate into the bubble during its expansion phase and through a complex series of events, over a number of bubble oscillations, reduce the core temperature of the collapsing bubble and hence the SL intensity.

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Acoustic emission from cavitating solutions: implications for the mechanisms of sonochemical reactions.

The acoustic emission from collapsing cavitation bubbles generated using ultrasound of 20 kHz and 515 kHz frequencies in water has been measured and correlated with sonoluminescence and hydroxyl radical production to yield further information on the frequency dependence of sonochemical reactions. A reasonable correlation was found, and the results suggest differences in the predominant types of cavitation observed under laboratory conditions.

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A comparison between multibubble sonoluminescence intensity and the temperature within cavitation bubbles.

Cavitation bubble temperatures have been measured using a methyl radical recombination method and compared with the changes in the sonoluminescence intensity in aqueous ethanol solutions over a range of concentrations. Whereas the sonoluminescence intensity was decreased by more than 90% at low ethanol concentrations (<0.1 M), the measured bubble temperatures seem to be unaffected at this level of additive. The cavitation bubble temperatures were noticeably decreased at substantially higher ethanol concentrations (0.5 M). It has been concluded that the methyl radical recombination method does not report on the true sonoluminescence temperatures. However, it does report on the average bubble temperatures at which sonochemical reactions occur.

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An experimental and theoretical study of competitive adsorption at the n-heptane/water interface.

A model to calculate the interfacial concentration of competing surface active species in a two-phase oil/water system was developed. To enable the calculation of the surface excess of 2-hydroxy-5-nonylacetophenone oxime (HNAPO, active ingredient of LIX 84) in the presence of surfactants competing for interfacial area, an interfacial adsorption competition model was derived for noninteracting surface active species in a n-heptane/aqueous system, assuming ideal enthalpy and entropy of mixing. The model was found to be valid for HNAPO in the presence of sodium dodecyl sulfate (SDS) or dodecyldimethyl(3-sulfopropyl)ammonium (DDSA). In the case of dodecyltrimethylammonium chloride (DTAC) or octa(ethylene glycol) mono-n-dodecyl ether (C12E8) as the competing surfactants with HNAPO, the predicted surface excess values from the model fit less favorably. The difference was shown to not be due to nonideal entropy of mixing.

Adsorption↗

The optimisation of ultrasonic cleaning procedures for dairy fouled ultrafiltration membranes.

Ultrafiltration (UF) of whey is a major membrane based process in the dairy industry. However, commercialization of this application has been limited by membrane fouling, which has a detrimental influence on the permeation rate. There are a number of different chemical and physical cleaning methods currently used for cleaning a fouled membrane. It has been suggested that the cleaning frequency and the severity of such cleaning procedures control the membrane lifetime. The development of an optimal cleaning strategy should therefore have a direct implication on the process economics. Recently, the use of ultrasound has attracted considerable interest as an alternative approach to the conventional methods. In the present study, we have studied the ultrasonic cleaning of polysulfone ultrafiltration membranes fouled with dairy whey solutions. The effects of a number of cleaning process parameters have been examined in the presence of ultrasound and results compared with the conventional operation. Experiments were conducted using a small single sheet membrane unit that was immersed totally within an ultrasonic bath. Results show that ultrasonic cleaning improves the cleaning efficiency under all experimental conditions. The ultrasonic effect is more significant in the absence of surfactant, but is less influenced by temperature and transmembrane pressure. Our results suggest that the ultrasonic energy acts primarily by increasing the turbulence within the cleaning solution.

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Estimation of ultrasound induced cavitation bubble temperatures in aqueous solutions.

Mean acoustic cavitation bubble temperatures have been measured in a series of aqueous solutions containing C(1)-C(5) aliphatic alcohols, at 355 kHz. The method relies on the distribution of hydrocarbon product yields produced from the recombination of methyl radicals generated on the thermal decomposition of the alcohols. The mean bubble temperature was found to decrease with increasing concentration of alcohol with the effect being more pronounced the higher the molecular weight (the lower the vapour pressure) of the alcohol. It is shown that the decrease in the temperatures measured correlates very well with an increase in the surface excess of the alcohol, similar to that previously reported for the quenching of sonoluminescence in aqueous solutions containing alcohols [J. Phys. Chem. B 101 (1997) 10845; J. Phys. Chem. B 103 (1999) 9231]. The measured temperatures ranged from 4600+/-200 K at zero alcohol concentration to 2300+/-200 K at 0.5 M t-butanol. The validity of the method is discussed and it is concluded that even though a number of assumptions need to be applied the results appear to indicate that the method gives an accurate measure of the mean bubble temperature.

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Interaction forces between oil-water particle interfaces--non-DLVO forces.

The interaction force between a rigid silica sphere and a butyl or octyl acetate droplet was measured in an aqueous environment using atomic force microscopy (AFM). The force measurements were performed without added stabilizers and the observed force behavior was found to be dependent on the type of inorganic electrolyte present, where the interfacial tension was constant over the electrolyte concentration range used. Force measurements in the presence of sodium nitrate showed repulsion at all concentrations. Force measurements in the presence of calcium nitrate or sodium perchlorate exhibited an initial repulsion followed by an attraction resulting in a mechanical instability in the AFM cantilever, termed jump-in. The force behavior observed was independent of the water solubility of the organic liquid, in that the same force-distance characteristics were obtained for slightly water soluble butyl acetate and the water sparingly soluble octyl acetate droplets. Modeling of the drop profile during particle-droplet interactions for this type of AFM measurement showed that the force-distance data for the sodium nitrate system obeys typical DLVO interactions. The disagreement between the DLVO predictions for the sodium perchlorate and calcium nitrate systems is attributed to a specific ion effect at the liquid-liquid interface, which gives rise to an attraction force that is greater than the electrostatic double layer repulsion over the length scale of 5 to 10 nm.

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Dynamics of the interaction forces at the silver/solution interface during amine adsorption.

The forces of interaction between a silver-coated particle and a flat silver surface in an aqueous medium were measured in the presence of a series of organic amines of varying concentrations. Atomic force microscopy (AFM) was used to quantify the replacement rate of adsorbed citrate molecules on the silver surfaces by a variety of amines, under conditions where the time scale of the amine adsorption was significantly slower than the time scale of the AFM measurements. The decay length of the electrostatic double-layer interaction between the silver surfaces was found to be time independent; thus, the change in surface change density (determined from the interaction forces) was used to quantify the replacement rate of adsorbed citrate by amine. In the absence of amine, the interaction force between the silver surfaces exhibited evidence of a multilayer structure of adsorbed citrate molecules on each silver surface. Upon addition of the amine, a decrease in the interaction force was always observed, where the dynamics of the force were dependent on both concentration and the molecular structure of the amine. These results are discussed with respect to formation of colloidal particles in synthesis routes where particle aggregation has a significant impact on the control of particle morphology and size.

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Forces between two oil drops in aqueous solution measured by AFM.

The surface and hydrodynamic forces between individual oil droplets in solution can provide insight into both emulsion stability and processes such as drop coalescence in liquid-liquid extraction. We present the first measurements of the interaction forces between alkane droplets in aqueous solution using atomic force microscopy. The radii of the droplets were well below the capillary lengths for the system, thus gravity effects are negligible, and interfacial tension and interaction forces governed the system behavior. The effects of modulating electrostatic double-layer interactions and interfacial tension through the presence of an anionic surfactant are demonstrated. Challenges in interpretation of the force data due to drop deformation are also discussed. A range of drop approach and retract speeds was used to determine the regime where hydrodynamic drainage effects had significant impact on the measurement.

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