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PubMed1998

[Usefulness of blood and plasma viscosity measurements in the evaluation of arteriopathic patients].

Blood viscosity represents the internal friction of the blood, in other terms, its resistance to be deformed and to flow under a tangential force. This function is conditioned by the intrinsic characteristics of blood and the geometry of the system in which flow occurs. Thus, any in vitro (or ex vivo) system of measurement of blood viscosity represents a relatively approximate evaluation of the ratio between intertial forces and viscous resistance. However, the possibility of measuring blood viscosity in a reproducible way provided the opportunity of identifying some clinical conditions associated with a worsening in rheologic parameters. Thus, "primary" and "secondary" hyperviscosity syndromes have been defined, on the basis of the pathogenetic responsibility of rheologic or hemodynamic factors, respectively. The possibility of performing in vitro measurement of blood viscosity provided the opportunity of planning several clinical pharmacology studies with theoretically active drugs. On such a basis, the rationale has arisen for a "rheologic therapy" of circulatory disturbances. Moreover, the evaluation of rheologic parameters is extremely useful since epidemiological studies have shown that viscosity may represent a marker and a prognostic factor for the progression of ischemic diseases as well as an independent risk factor, thus suggesting the opportunity of performing controlled clinical studies to evaluate the impact of hemorheological changes in the prevention of cardiovascular events.

Blood Flow Velocity↗
PubMed1998

Direct Determination of the Dependence of the Surface Shear and Dilatational Viscosities on the Thermodynamic State of the Interface: Theoretical Foundations.

Recent developments in nonlinear optical techniques for noninvasive probing of a surfactant influenced gas/liquid interface allow for the measurement of the surfactant surface concentration, c, and thus provide new opportunities for the direct determination of its intrinsic viscosities. Here, we present the theoretical foundations, based on the Boussinesq-Scriven surface model without the usual simplification of constant viscosities, for an experimental technique to directly measure the surface shear (µs) and dilatational (kappas) viscosities of a Newtonian interface as functions of the surfactant surface concentration. This ability to directly measure the surfactant concentration permits the use of a simple surface flow for the measurement of the surface viscosities. The requirements are that the interface must be nearly flat, and the flow steady, axisymmetric, and swirling; these flow conditions can be achieved in the deep-channel viscometer driven at relatively fast rates. The tangential stress balance on such an interface leads to two equations; the balance in the azimuthal direction involves only µs and its gradients, and the balance in the radial direction involves both µs and kappas and their gradients. By further exploiting recent developments in laser-based flow measuring techniques, the surface velocities and their gradients which appear in the two equations can be measured directly. The surface tension gradient, which appears in the radial balance equation, is incorporated from the equation of state for the surfactant system and direct measurements of the surfactant surface concentration distribution. The stress balance equations are then ordinary differential equations in the surface viscosities as functions of radial position, which can be readily integrated. Since c is measured as a function of radial position, we then have a direct measurement of µs and kappas as functions of c. Numerical computations of the Navier-Stokes equations are performed to determine the appropriate conditions to achieve the requisite secondary flow. Copyright 1998 Academic Press.

Journal Article↗
PubMed1999

Role of Electrostatic Repulsion on the Viscosity of Bidisperse Silica Suspensions.

The flow behavior of bidisperse aqueous silica suspensions has been studied at different electrolyte concentrations as a function of shear rate, total volume fraction of the particles, and volume ratio of small to large particles. It is shown that the range of the electrostatic repulsion plays an important role in determining the viscosity of the suspension. Binary mixtures of particles of longer range repulsive forces showed higher viscosities than the suspensions of shorter range electrostatic interactions. Bimodal suspensions of long-range interactions showed non-Newtonian behavior over wider ranges of shear due to the deformation of the ionic cloud around the particles, which is larger in these systems. The viscosity of bimodal suspensions used in this study was scaled with respect to the viscosity of the related monosized systems and the viscosity of one bimodal suspension at a fixed total volume fraction of the particles, employing our earlier scaling method. The model normalizes the effect of colloidal forces by introducing a scaling factor that collapses the data into a single curve for bimodal suspensions of a particular size ratio, and it is shown that the model is valid for systems with both short-range and long-range repulsive forces. Copyright 1999 Academic Press.

Journal Article↗
PubMed1991

The coupling of catalytically relevant conformational fluctuations in subtilisin BPN' to solution viscosity revealed by hydrogen isotope exchange and inhibitor binding.

We have measured the tritium outexchange of subtilisin BPN'. A consistent and rather small group of hydrogens was isolated by their sensitivity to inhibitor binding. The viscosity dependence of exchange from these inhibitor protected hydrogens was then examined in 0.05 M MES buffer, pH 6.5 and 10 degrees C. The viscosity of the reaction medium was varied by added glycerol and ethylene glycol. The exchange rates were corrected to be compared at identical hydroxyl ion and water activity. The salient observation is the strikingly similar viscosity coupling behavior when compared to the deacylation step of ester hydrolysis catalyzed by the same enzyme (Ng and Rosenberg, Biophysical Chemistry, 39 (1991) 57). We have obtained a viscosity coupling constant of 0.68 -/+ 0.18 for hydrogen exchange in glycerol (cf. 0.65 -/+ 0.11 for deacylation in glycerol, sucrose, glucose and fructose); 1.67 -/+ 0.07 for outexchange (cf. 1.92 -/+ 0.09 for deacylation), in the presence of ethylene glycol. The two reactions are very chemically dissimilar, yet they show very similar viscosity coupling behavior. This together with the well established role of structural fluctuations in hydrogen exchange implies a similar role of structural fluctuations in the deacylation step of subtilisin BPN' catalyzed ester hydrolysis.

Journal Article↗
PubMed2004

The shear viscosity of polyampholyte (gelatin) stabilized colloidal dispersions.

A micromechanical model for the zero shear viscosity of polyampholyte-stabilized colloidal dispersions based on the osmotic overlap potential is proposed and tested against model system measurements. This model relates the shear viscosity of polyampholyte-stabilized colloidal dispersions to the oncotic pressure of polyampholyte solutions through an interparticle potential and an effective hard-sphere scaling. The results of viscosity calculations based on independently measured parameters compare favorably to experimental measurements on model, silica dispersions stabilized with adsorbed photographic grade gelatin. The results support a direct link between the capacity of polyampholytes and polyelectrolytes to stabilize dispersions and control dispersion viscosity and their solution oncotic pressure. The model is also demonstrated to provide a master curve for literature data for the zero shear viscosity of polyampholyte stabilized colloidal dispersions.

Journal Article↗
PubMed2005

Remarks on the shear viscosity of surfaces stabilised with soluble surfactants.

A survey is made of previously reported values of the surface shear viscosity of sodium dodecyl sulphate solution which reveals inconsistencies. The origin of these inconsistencies is thought to be due to the fact that, because SDS is a soluble surfactant, the surface deformation rate is governed by a three-dimensional sublayer adjacent to the surface and is therefore inherently experiment-dependent. Because of this, only an apparent surface shear viscosity that is specific to a particular experiment can be measured. However, for an insoluble surfactant, an intrinsic two-dimensional surface viscosity can be clearly defined. Some methods of measuring an apparent surface shear viscosity assume that the surface shear viscosity is the only surface property that determines the drainage rate from foam or individual Plateau borders but there is experimental evidence to show that other surface properties may be significant.

Letter↗
PubMed1997

Fluorogenic compound hydrolysis as a measure of toxicity-induced cytoplasmic viscosity and pH changes.

If a fluorogenic compound, such as fluorescein diacetate, is added to a water solution containing living cells it becomes hydrolyzed by intracellular esterases into a fluorochrome whose fluorescence can be used to monitor the cytoplasmic pH and the cytoplasmic viscosity of the cells. In this paper we have used this technique to measure the effects of different concentrations of Co2+ and Cd2+ ions on the cytoplasmic pH and the cytoplasmic viscosity of a single cell culture. Our results indicate that the observed decrease in the efficiency of the intracellular hydrolyzation of fluorogenic substances in the presence of different concentrations of heavy metals could be caused by both a decrease in the cytoplasmic pH and an increase in the cytoplasmic viscosity. A decrease in cytoplasmic pH would decrease the effectiveness of the intracellular enzymes, whereas an increase in cytoplasmic viscosity would decrease diffusion which would also reduce the effectiveness of the reaction. The dependence of the reciprocal of the cytoplasmic viscosity on the concentration of these metals correlates well with published results on their toxicity.

Journal Article↗
PubMed2005

Modified free volume theory of self-diffusion and molecular theory of shear viscosity of liquid carbon dioxide.

In previous work on the density fluctuation theory of transport coefficients of liquids, it was necessary to use empirical self-diffusion coefficients to calculate the transport coefficients (e.g., shear viscosity of carbon dioxide). In this work, the necessity of empirical input of the self-diffusion coefficients in the calculation of shear viscosity is removed, and the theory is thus made a self-contained molecular theory of transport coefficients of liquids, albeit it contains an empirical parameter in the subcritical regime. The required self-diffusion coefficients of liquid carbon dioxide are calculated by using the modified free volume theory for which the generic van der Waals equation of state and Monte Carlo simulations are combined to accurately compute the mean free volume by means of statistical mechanics. They have been computed as a function of density along four different isotherms and isobars. A Lennard-Jones site-site interaction potential was used to model the molecular carbon dioxide interaction. The density and temperature dependence of the theoretical self-diffusion coefficients are shown to be in excellent agreement with experimental data when the minimum critical free volume is identified with the molecular volume. The self-diffusion coefficients thus computed are then used to compute the density and temperature dependence of the shear viscosity of liquid carbon dioxide by employing the density fluctuation theory formula for shear viscosity as reported in an earlier paper (J. Chem. Phys. 2000, 112, 7118). The theoretical shear viscosity is shown to be robust and yields excellent density and temperature dependence for carbon dioxide. The pair correlation function appearing in the theory has been computed by Monte Carlo simulations.

Journal Article↗
PubMed2006

Diffusion and viscosity in a crowded environment: from nano- to macroscale.

Although water is the chief component of living cells, food, and personal care products, the supramolecular components make their viscosity larger than that of water by several orders of magnitude. Using fluorescence correlation spectroscopy (FCS), photon correlation spectroscopy (PCS), NMR, and rheology data, we show how the viscosity changes from the value for water at the molecular scale to the large macroviscosity. We determined the viscosity experienced by nanoprobes (of sizes from 0.28 to 190 nm) in aqueous micellar solution of hexaethylene-glycol-monododecyl-ether (in a range of concentration from 0.1% w/w to 35% w/w) and identified a clear crossover at the length scale of 17 +/- 2 nm (slightly larger than persistence length of micelles) at which viscosity acquires its macroscopic value. The sharp dependence of the viscosity coefficients on the size of the probe in the nanoregime has important consequences for diffusion-limited reactions in crowded environments (e.g., living cells).

Journal Article↗
PubMed2004

Periodic change of viscosity and density in an oscillating chemical reaction.

It was found that the periodic change of the solution viscosity and density was generated in the Belousov-Zhabotinsky (BZ) reaction. This rhythmic phenomenon was observed in both the iron catalyst [[Fe(Phen)(3)](2+)-[Fe(Phen)(3)](3+)] and the cerium catalyst [Ce(III)-Ce(IV)] system, where the solution viscosity and density were synchronized with the redox potential in the in-phase mode. However, the time delay existed between the redox potential and the solution viscosity and density. The behavior of the BZ reaction was also monitored in the presence of the nonionic surfactant. This experiment revealed that, beyond the critical micelle concentration, the phase between the redox potential and the solution viscosity and density was synchronized into the antiphase mode. We suggested that the variation of the catalyst drove the oscillation of the solution viscosity and density in the BZ reaction.

Journal Article↗
PubMed2004

Temperature dependence of density, thermal expansion coefficient and shear viscosity of supercooled glycerol as a reflection of its structure.

The relationship of the microstructure of supercooled, highly viscous glycerol to the temperature dependence of its density, thermal expansion coefficient, and shear viscosity are discussed. The character of this temperature dependence at the transition from low viscosity state to the solid amorphous state (solidified state without nuclei) is described with help of function psi, which can be interpreted as the effective number of degrees of freedom responsible for the change of viscosity of glycerol over a broad range; these degrees of freedom are those related to the alpha-relaxation process. It is shown that the change in effective activation energy of the viscosity is completely determined by the parameter psi. The change in the shear viscosity of glycerol due to the influence of the solid-phase nuclei is considered. It is shown that the introduction of the parameter phi, equal to the specific volume occupied by the nuclei of the solid phase, together with psi provides a natural explanation of the temperature dependence of density and thermal expansion coefficients of glycerol in its liquid, solid amorphous, glassy, and crystal states. The peculiarities of the temperature dependence of phi(T) and psi(T) for glycerol and o-terphenyl are compared.

Journal Article↗
PubMed2004

Viscosity of confined inhomogeneous nonequilibrium fluids.

We use the nonlocal linear hydrodynamic constitutive model, proposed by Evans and Morriss [Statistical Mechanics of Nonequilibrium Liquids (Academic, London, 1990)], for computing an effective spatially dependent shear viscosity of inhomogeneous nonequilibrium fluids. The model is applied to a simple atomic fluid undergoing planar Poiseuille flow in a confined channel of several atomic diameters width. We compare the spatially dependent viscosity with a local generalization of Newton's law of viscosity and the Navier-Stokes viscosity, both of which are known to suffer extreme inaccuracies for highly inhomogeneous systems. The nonlocal constitutive model calculates effective position dependent viscosities that are free from the notorious singularities experienced by applying the commonly used local constitutive model. It is simple, general, and has widespread applicability in nanofluidics where experimental measurement of position dependent transport coefficients is currently inaccessible. In principle the method can be used to predict approximate flow profiles of any arbitrary inhomogeneous system. We demonstrate this by predicting the flow profile for a simple fluid undergoing planar Couette flow in a confined channel of several atomic diameters width.

Journal Article↗
PubMed2000

Effective viscosity of dense colloidal crystals

An exact scheme is presented to determine the effective viscosity tensor for periodic arrays of hard spherical particles suspended in a Newtonian fluid. In the highly symmetric case of cubic lattices this tensor is characterized by only two parameters. These parameters are calculated numerically for the three cubic lattice types and for the whole range of volume fractions. The correctness of the present method and its numerical implementation is confirmed by a comparison with the numerical and analytical results known from the literature. Some regular terms are determined that enter singular perturbation expansions suitable for high concentrations. Previous results for these terms are shown to be highly inaccurate. The modified expansions approach the exact numerical results over a range of densities extending to relatively low concentrations. The effective viscosity is examined for simple tetragonal (st) lattices and the results for various structures of the st type can be qualitatively understood on the basis of the motion of the spheres in response to the ambient shear flow. The angular velocity of the spheres-relative to the shear flow-is shown to be nonzero for certain orientations of the st lattice with respect to the shear flow, in contrast to what has been known for cubic arrays. Finite viscosities are found in most cases where the particles are in contact as they are allowed to move in either rigid planar or linelike structures, or they can perform a smooth rolling motion. The only occurrence where the viscosity diverges for a st structure, or equally any other Bravais lattice, is for the case of close packing. Moreover, the concentration-dependent shear viscosity is determined for a variety of microstructures and the results are compared with recent data obtained from experiments on ordered hard-sphere suspensions.

Journal Article↗
PubMed2002

Viscosity bifurcation in granular materials, foams, and emulsions.

We show that the rheological properties of dry granular materials, as well as foams and emulsions, are similar to typical thixotropic fluids: under a sufficiently strong shear the viscosity decreases in time, leading to a hysteresis in an up-and-down stress ramp. This leads to a viscosity bifurcation around a critical stress: for smaller stresses, the viscosity increases in time and the material eventually stops flowing, whereas for slightly larger stresses the viscosity decreases continuously with time and the flow accelerates. These results show that all jammed systems exhibit strong mechanical similarities around the transition between a "fluid" and a "solid" state, and that the transition between these states is discontinuous. This similarity is further emphasized by the fact that both a simple model for the dynamics of a grain on a sandpile [Quartier et al., Phys. Rev. E 62, 8299 (2000)] and a simple model for the thixotropic behavior of (colloidal) pastes [Coussot et al., Phys. Rev. Lett. 88, 175501 (2002)] extrapolated to granular flows qualitatively predict this viscosity bifurcation.

Journal Article↗
PubMed2003

Shear viscosity relaxation of a critical binary liquid.

Two series of diffusion coefficients D are reported for the triethylamine-water binary critical mixture. One has been obtained from quasielastic light scattering measurements, the other one has been derived from broadband ultrasonic spectra, yielding the relaxation rate of order parameter fluctuations, and shear viscosity data. Using high frequency shear impedance spectrometry in the range 20-130 MHz, relaxations in the background part of the viscosity, resulting in viscoelastic mixture properties, have been found. Both series of D data agree either if a half-attenuation frequency distinctly smaller than the theoretical value Omega(1/2)=2.1 is used in the Bhattacharjee-Ferrell scaling function or if the viscosity extrapolated from the shear impedance measurements to low frequencies is applied to the Kawasaki-Ferrell relation. This extrapolated viscosity is smaller than the static shear viscosity measured with capillary viscosimeters.

Journal Article↗
PubMed2004

Simultaneous free-volume modeling of the self-diffusion coefficient and dynamic viscosity at high pressure.

In this work, a simultaneous modeling of the self-diffusion coefficient and the dynamic viscosity is presented. In the microstructural theory these two quantities are governed by the same friction coefficient related to the mobility of the molecule. A recent free-volume model, already successfully applied to dynamic viscosity, has been considered and generalized. In this generalized model the compound is characterized by only four parameters. But if the quadratic length is known, the number of adjustable parameters is three. The compounds considered in this work are benzene, carbon tetrachloride, chlorotrifluoromethane, cyclohexane, methylcyclohexane, and tetramethylsilane. For these pure compounds we have found in the literature several data for both the self-diffusion and the dynamic viscosity in large viscosity, diffusion, temperature, and pressure intervals (up to around 500 MPa for methylcyclohexane and tetramethylsilane). The average absolute deviation obtained by the modeling is generally less than 3% for the viscosity and 5% for the self-diffusion.

Journal Article↗
PubMed2005

Viscosity anomaly near the critical point in nitrobenzene + alkane binary systems.

The viscosity near the critical point in nitrobenzene+hexane and nitrobenzene+heptane binary systems was studied by examining the viscosity values for critical mixtures at a variable temperature as obtained with a falling-ball viscometer. The regular part of the viscosity of the critical mixtures was calculated by interpolating measurements made at noncritical concentrations. Because viscosity anomaly studies must be conducted at zero shear, a method allowing the estimation of the effective shear for this type of viscometer was developed with a view to introducing the corrections required. This methodology was used to determine the critical exponent for the viscosity anomaly in nitrobenzene+hexane and nitrobenzene+heptane systems, which were found to be 0.0422+/-0.0004 and 0.0432+/-0.0013 , respectively, very consistent with the accepted value: 0.043.

Journal Article↗
PubMed1992

Viscosity and social cohesion in temporal lobe epilepsy.

Clinical case reports suggest that viscosity, the behavioural tendency to talk repetitively and circumstantially about a restricted range of topics, is common in patients with temporal lobe epilepsy (TLE). Such patients are also reported to exhibit heightened levels of social cohesion, the tendency to become interpersonally "clingy". This "sticky" interpersonal style may be particularly common in TLE patients with a left sided temporal lobe seizure focus. To test this hypothesis, self-report and observer rating scales were developed to assess both viscosity and social cohesion. Subjects consisted of patients with right, left, or bilateral temporal lobe seizure foci, absence or primary generalised tonic-clonic seizures, psychiatric controls (panic disorder patients), and normal controls. Elevations on the viscosity scale were observed primarily in TLE patients with left or bilateral seizure foci. Viscosity scores also correlated with seizure duration and left handedness. No group differences were observed on the social cohesion scale. These findings are consistent with the hypothesis that viscosity results from subtle interictal language disturbances, although other pathogenetic mechanisms are discussed.

Anomia↗