Capillary break-up rheometry of low-viscosity elastic fluids

We investigate the dynamics of the capillary thinning and break-up process for low viscosity elastic fluids such as dilute polymer solutions. Standard measurements of the evolution of the midpoint diameter of the necking fluid filament are augmented by high speed digital video images of the break up dynamics. We show that the successful operation of a capillary thinning device is governed by three important time scales (which characterize the relative importance of inertial, viscous and elastic processes), and also by two important length scales (which specify the initial sample size and the total stretch imposed on the sample). By optimizing the ranges of these geometric parameters, we are able to measure characteristic time scales for tensile stress growth as small as 1 millisecond for a number of model dilute and semi-dilute solutions of polyethylene oxide (PEO) in water and glycerol. If the final aspect ratio of the sample is too small, or the total axial stretch is too great, measurements are limited, respectively, by inertial oscillations of the liquid bridge or by the development of the well-known beads-on-a-string morphology which disrupt the formation of a uniform necking filament. By considering the magnitudes of the natural time scales associated with viscous flow, elastic stress growth and inertial oscillations it is possible to construct an operability diagram characterizing successful operation of a capillary break-up extensional rheometer. For Newtonian fluids, viscosities greater than approximately 70 mPas are required; however for dilute solutions of high molecular weight polymer, the minimum Viscosity is substantially lower due to the additional elastic stresses arising from molecular extension. For PEO of molecular weight 2.10(6) g/mol, it is possible to measure relaxation times of order 1 ms in dilute polymer solutions with zero-shear-rate viscosities on the order of 2-10 mPas.

Tyrosine 394 is phosphorylated in Alzheimer's paired helical filament tau and in fetal tau with c-Abl as the candidate tyrosine kinase

Tau is a major microtubule-associated protein of axons and is also the principal component of the paired helical filaments (PHFs) that comprise the neurofibrillary tangles found in Alzheimer's disease and other tauopathies. Besides phosphorylation of tau on serine and threonine residues in both normal tau and tau from neurofibrillary tangles, Tyr-18 was reported to be a site of phosphorylation by the Src-family kinase Fyn. We examined whether tyrosine residues other than Tyr-18 are phosphorylated in tau and whether other tyrosine kinases might phosphorylate tau. Using mass spectrometry, we positively identified phosphorylated Tyr-394 in PHF-tau from an Alzheimer brain and in human fetal brain tau. When wild-type human tau was transfected into fibroblasts or neuroblastoma cells, treatment with pervanadate caused tau to become phosphorylated on tyrosine by endogenous kinases. By replacing each of the five tyrosines in tau with phenylalanine, we identified Tyr-394 as the major site of tyrosine phosphorylation in tau. Tyrosine phosphorylation of tau was inhibited by PP2 (4-amino-5-(4-chlorophenyl-7-(t-butyl) pyrazolo[3,4-d] pyrimidine), which is known to inhibit Src-family kinases and c-Abl. Cotransfection of tau and kinases showed that Tyr-18 was the major site for Fyn phosphorylation, but Tyr-394 was the main residue for Abl. In vitro, Abl phosphorylated tau directly. Abl could be coprecipitated with tau and was present in pretangle neurons in brain sections from Alzheimer cases. These results show that phosphorylation of tau on Tyr-394 is a physiological event that is potentially part of a signal relay and suggest that Abl could have a pathogenic role in Alzheimer's disease.

Adsorption of Lennard-Jones fluids in carbon slit pores of a finite length. A computer simulation study

The adsorption of simple Lennard-Jones fluids in a carbon slit pore of finite length was studied with Canonical Ensemble (NVT) and Gibbs Ensemble Monte Carlo Simulations (GEMC). The Canonical Ensemble was a collection of cubic simulation boxes in which a finite pore resides, while the Gibbs Ensemble was that of the pore space of the finite pore. Argon was used as a model for Lennard-Jones fluids, while the adsorbent was modelled as a finite carbon slit pore whose two walls were composed of three graphene layers with carbon atoms arranged in a hexagonal pattern. The Lennard-Jones (LJ) 12-6 potential model was used to compute the interaction energy between two fluid particles, and also between a fluid particle and a carbon atom. Argon adsorption isotherms were obtained at 87.3 K for pore widths of 1.0, 1.5 and 2.0 nm using both Canonical and Gibbs Ensembles. These results were compared with isotherms obtained with corresponding infinite pores using Grand Canonical Ensembles. The effects of the number of cycles necessary to reach equilibrium, the initial allocation of particles, the displacement step and the simulation box size were particularly investigated in the Monte Carlo simulation with Canonical Ensembles. Of these parameters, the displacement step had the most significant effect on the performance of the Monte Carlo simulation. The simulation box size was also important, especially at low pressures at which the size must be sufficiently large to have a statistically acceptable number of particles in the bulk phase. Finally, it was found that the Canonical Ensemble and the Gibbs Ensemble both yielded the same isotherm (within statistical error); however, the computation time for GEMC was shorter than that for canonical ensemble simulation. However, the latter method described the proper interface between the reservoir and the adsorbed phase (and hence the meniscus).

Adsorption of pure fluids in activated carbon with a modified lattice gas model

In this article we study the effects of adsorbed phase compression, lattice structure, and pore size distribution on the analysis of adsorption in microporous activated carbon. The lattice gas approach of Ono-Kondo is modified to account for the above effects. Data of nitrogen adsorption at 77 K onto a number of activated carbon samples are analyzed to investigate the pore filling pressure versus pore width, the packing effect, and the compression of the adsorbed phase. It is found that the PSDs obtained from this analysis are comparable to those obtained by the DFT method. The discrete nature of the PSDs derived from the modified lattice gas theory is due to the inherent assumption of discrete layers of molecules. Nevertheless, it does provide interesting information on the evolution of micropores during the activation process.

Differences in surfactant lipids collected from pleural and pulmonary lining fluids

Purpose. The type and relative importance of saturated and unsaturated phospholipid components of surfactant within the epithelial lining fluid (ELF) of the inner and outer surfaces of the lung is not known. Methods. Seven healthy dogs were anesthetized and a bronchoalveolar lavage (BAL) was performed, immediately followed by a pleural lavage (PL). Lipid was extracted from lavage fluid and then analyzed for saturated, primarily dipalmitoylphosphatidylcholine (DPPC), and unsaturated phosphatidylcholine (PC) species using high-performance liquid chromatography (HPLC) with combined fluorescence and ultraviolet detection. Dilution of ELF in lavage fluids was corrected for using the urea method. Results. DPPC (494.7 +/- 213.9 mu g/mL) was the predominant PC present in ELF collected from the alveolar surface. In contrast, significantly higher (p = 0.028) proportions of unsaturated PC species were measured in PL fluid (similar to 105 mu g/mL), particularly stearoyl-linoleoyl-phosphatidylcholine (SLPC), which could not be measured in fluid collected from the alveoli, compared to DPPC (2.6 +/- 2.0 mu g/mL). Conclusions. This study indicates that unsaturated PC species seem to be more important than saturated species, particularly DPPC, in the pleural cavity, which has implications for surfactant replenishment following pleural disease or thoracic surgery.

Using urea dilution to standardise components of pleural and bronchoalveolar lavage fluids in the dog

AIM: To develop a technique to estimate the volume of epithelial lining fluid (ELF) obtained during bronchoalveolar lavage (BAL) and pleural lavage (PL) in the dog, using the urea dilution method. METHODS: BAL and PL fluids were obtained by saline lavage of pulmonary and pleural cavities of nine clinically healthy mixed-breed dogs immediately after euthanasia. Cell counts in the BAL and PL fluids were measured using standard techniques. The concentration of ELF in each lavage fluid was calculated from the relative concentration of urea in plasma and in each type of lavage fluid. Cell counts in ELF were then calculated. RESULTS: There were substantially higher cell counts in ELF compared to BAL or PF fluid. However, nucleated cell counts in ELF could not be predicted from cell counts in BAL or PL fluid. CONCLUSIONS AND CLINICAL RELEVANCE: These results suggest that accurate assessment of cellular or non-cellular components in lavage fluids should include a calculation of the proportion of ELF recovered, using a method such as urea dilution.

A trace element study of siderite-jasper banded iron formation in the 3.45 Ga Warrawoona Group, Pilbara Craton - Formation from hydrothermal fluids and shallow seawater

Shale-normalised rare earth element and yttrium (REE + Y) patterns for siderite-jasper couples in a banded iron formation of the 3.45 Ga Panorama Formation, Warrawoona Group, eastern Pilbara Craton, display distinct positive Y and Eu anomalies and weak positive La and Gd anomalies, combined with depleted light REE relative to middle and heavy REE. Ambient seawater and hydrothermal fluids are identified as major sources of REE + Y for the BIF. In the case of siderites, strong correlations between incompatible trace elements and trace element ratios diagnostic of seawater indicate variable input from a terrigenous source (e.g. volcanic ash). We propose a volcanic caldera setting as a likely depositional environment where jasper and siderite precipitated as alternating bands in response to episodic changes in ambient water chemistry. The episodicity was either driven by fluctuations in the intensity of hydrothermal activity or changes in magma chamber activity, which in turn controlled relative sea level. In this context, precipitation of jasper probably reflects background conditions during which seawater was saturated in silica due to evaporative conditions, while siderites were deposited most likely during intermittent periods of enhanced volcanic activity when seawater was more acidic due to the release of exhalative phases (e.g. CO2). © 2005 Elsevier B.V. All rights reserved.

Bajo de la Alumbrera copper-gold deposit: Stable isotope evidence for a porphyry-related hydrothermal system dominated by magmatic aqueous fluids

Alteration zones at the gold-rich Bajo de la Alumbrera porphyry copper deposit in northwestern Argentina are centered on several porphyritic intrusions. They are zoned from a central copper-iron sulfide and gold-mineralized potassic (biotite-K-feldspar +/- quartz) core outward to propylitic (chlorite-illite-epidote-calcite) assemblages. A mineralized intermediate argillic alteration assemblage (chlorite-illite +/- pyrite) has overprinted the potassic alteration zone across the top and sides of the deposit and is itself zoned outward into phyllic (quartzinuscovite-illite +/- pyrite) alteration. This study contributes new data to previously reported delta(18)O and delta D compositions of fluids responsible for the alteration at Bajo de la Alumbrera, and the data are used to infer likely ore-forming processes. Measured and calculated delta(18)O and delta D values of fluids (+8.3 to +10.2 and -33 to -81 parts per thousand, respectively) confirm a primary magmatic origin for the earliest potassic alteration phase. Lower temperature potassic alteration formed from magmatic fluids with lower delta D values (down to -123 parts per thousand). These depleted compositions are distinct from meteoric water and consistent with degassing and volatile exsolution of magmatic fluids derived from an underlying magma. Variability in the calculated composition of fluid associated with potassic alteration is explained in terms of phase separation (or boiling). if copper-iron sulfide deposition occurred during cooling (as proposed elsewhere), this cooling was largely a result of phase separation. Magmatic water was directly involved in the formation of overprinting intermediate argillic alteration assemblages at Bajo de la Alumbrera. Calculated delta(18)O and delta D values of fluids associated with this alteration range from +4.8 to +8.1 and -31 to -71 per mil, respectively Compositions determined for fluids associated with phyllic alteration (-0.8 to +10.2 and -31 to -119 parts per thousand) overlap with the values determined for the intermediate argillic alteration. We infer that phyllic alteration assemblages developed during two stages; the first was a high-temperature (400 degrees-300 degrees C) stage with D-depleted water (delta D = -66 to -119 parts per thousand). This compositional range may have resulted from magma degassing and/or the injection of new magmatic water into a compositionally evolved hydrothermal system. The isotopic variations also can be explained by increased fluid-rock interaction. The second stage of phyllic alteration occurred at a lower temperature (similar to 200 degrees C), and variations in the modeled isotopic compositions imply mixing of magmatic and meteoric waters. Ore deposition that occurred late in the evolution of the hydrothermal system was probably associated with further cooling of the magmatic fluid, in part caused by fluid-rock interaction and phase separation. Changing pH and/or oxygen fuoracity may have caused additional ore deposition. The ingress of meteoric water appears to postdate the bulk of mineralization and occurred as the system at Bajo de la Alumbrera waned.

Pendant drop formation of shear-thinning and yield stress fluids

A volume-of-fluid numerical method is used to predict the dynamics of shear-thinning liquid drop formation in air from a circular orifice. The validity of the numerical calculation is confirmed for a Newtonian liquid by comparison with experimental measurements. For particular values of Weber number and Froude number, predictions show a more rapid pinch-off, and a reduced number of secondary droplets, with increasing shear-thinning. Also a minimum in the limiting drop length occurs for the smallest Weber number as the zero-shear viscosity is varied. At the highest viscosity, the drop length is reduced due to shear-thinning, whereas at lower viscosities there is little effect of shear-thinning. The evolution of predicted drop shape, drop thickness and length, and the configuration at pinch-off are discussed for shear-thinning drops. The evolution of a drop of Bingham yield stress liquid is also considered as a limiting case. In contrast to the shear-thinning cases, it exhibits a plug flow prior to necking, an almost step-change approach to pinch-off of a torpedo shaped drop following the onset of necking, and a much smaller neck length; no secondary drops are formed. The results demonstrate the potential of the numerical model as a design tool in tailoring the fluid rheology for controlling drop formation behaviour. (c) 2006 Elsevier Inc. All rights reserved.

The effects of energy sites on adsorption of Lennard–Jones fluids and phase transition in carbon slit pore of finite length a computer simulation study

A Monte Carlo simulation method is Used 10 study the effects of adsorption strength and topology of sites on adsorption of simple Lennard-Jones fluids in a carbon slit pore of finite length. Argon is used as a model adsorbate, while the adsorbent is modeled as a finite carbon slit pore whose two walls composed of three graphene layers with carbon atoms arranged in a hexagonal pattern. Impurities having well depth of interaction greater than that of carbon atom are assumed to be grafted onto the surface. Different topologies of the impurities; corner, centre, shelf and random topologies are studied. Adsorption isotherms of argon at 87.3 K are obtained for pore having widths of 1, 1.5 and 3 11111 using a Grand Canonical Monte Carlo simulation (GCMC). These results are compared with isotherms obtained for infinite pores. It is shown that the Surface heterogeneity affects significantly the overall adsorption isotherm, particularly the phase transition. Basically it shifts the onset of adsorption to lower pressure and the adsorption isotherms for these four impurity models are generally greater than that for finite pore. The positions of impurities on solid Surface also affect the shape of the adsorption isotherm and the phase transition. We have found that the impurities allocated at the centre of pore walls provide the greatest isotherm at low pressures. However when the pressure increases the impurities allocated along the edges of the graphene layers show the most significant effect on the adsorption isotherm. We have investigated the effect of surface heterogeneity on adsorption hysteresis loops of three models of impurity topology, it shows that the adsorption branches of these isotherms are different, while the desorption branches are quite close to each other. This suggests that the desorption branch is either the thermodynamic equilibrium branch or closer to it than the adsorption branch. (c) 2005 Elsevier Inc. All rights reserved.

Clinicians' evaluations of fetal oximetry sensor placement in a multicentre randomised trial (the FOREMOST trial)

Background: Fetal pulse oximetry (FPO) may improve the assessment of the fetal well-being in labour. Reports of health-care provider's evaluations of new technology are important in the overall evaluation of that technology. Aims: To determine doctors' and midwives' perceptions of their experience placing FPO sensors. Methods: We surveyed clinicians (midwives and doctors) following placement of a FPO sensor during the FOREMOST trial (multicentre randomised trial of fetal pulse oximetry). Clinicians rated ease of sensor placement (poor, fair, good and excellent). Potential influences on ease of sensor placement (staff category, prior experience in Birth Suite, prior experience in placing sensors, epidural analgesia, cervical dilatation and fetal station) were examined by ordinal regression. Results: There were 281 surveys returned for the 294 sensor placement attempts (response rate 96%). Sensors were placed by midwives (29%), research midwives (48%), registrars (22%) and obstetricians (1%). The majority of clinicians had 1 or more years' Birth Suite experience, had placed six or more sensors previously, and rated ease of sensor placement as good. Advancing fetal station (P < 0.001) and the presence of epidural analgesia prior to sensor placement (P = 0.029) predicted improved ease of sensor placement. Having a clinician placing a sensor for the first time predicted a lower rating for ease of sensor placement (P = 0.001), compared to having placed one or more sensors previously. Conclusions: Clinicians with varying levels of Birth Suite experience successfully placed fetal oxygen saturation sensors, with the majority rating ease of sensor placement as good.