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Transport properties of partially ionized and unmagnetized plasmas.

This work is a comprehensive and theoretical study of transport phenomena in partially ionized and unmagnetized plasmas by means of kinetic theory. The pros and cons of different models encountered in the literature are presented. A dimensional analysis of the Boltzmann equation deals with the disparity of mass between electrons and heavy particles and yields the epochal relaxation concept. First, electrons and heavy particles exhibit distinct kinetic time scales and may have different translational temperatures. The hydrodynamic velocity is assumed to be identical for both types of species. Second, at the hydrodynamic time scale the energy exchanged between electrons and heavy particles tends to equalize both temperatures. Global and species macroscopic fluid conservation equations are given. New constrained integral equations are derived from a modified Chapman-Enskog perturbative method. Adequate bracket integrals are introduced to treat thermal nonequilibrium. A symmetric mathematical formalism is preferred for physical and numerical standpoints. A Laguerre-Sonine polynomial expansion allows for systems of transport to be derived. Momentum, mass, and energy fluxes are associated to shear viscosity, diffusion coefficients, thermal diffusion coefficients, and thermal conductivities. A Goldstein expansion of the perturbation function provides explicit expressions of the thermal diffusion ratios and measurable thermal conductivities. Thermal diffusion terms already found in the Russian literature ensure the exact mass conservation. A generalized Stefan-Maxwell equation is derived following the method of Kolesnikov and Tirskiy. The bracket integral reduction in terms of transport collision integrals is presented in Appendix for the thermal nonequilibrium case. A simple Eucken correction is proposed to deal with the internal degrees of freedom of atoms and polyatomic molecules, neglecting inelastic collisions. The authors believe that the final expressions are readily usable for practical applications in fluid dynamics.

Journal Article↗

Ruthenium Carbonyl Clusters in Faujasite Cages: Synthesis and Characterization.

The synthesis of the intrafaujasite anchoring of ruthenium carbonyl clusters involves the adsorption of metal carbonyl species or metal ion exchange into faujasite cages followed by reductive carbonylation under an atmosphere of CO and H(2). The characterization of the structure and properties of these samples was based on a multianalytical approach, including FT-IR, UV-vis, PXRD, and EXAFS spectroscopies, CO/H(2) gas chemisorption, and (13)CO isotopic exchange. From this study, several key points emerge. (a) [Ru(3)(CO)(12)] clusters thermally diffused into dehydrated faujasite cages. (b) [Ru(3)(CO)(12)] guests in Na(56)Y were thermally activated, in a hydrogen atmosphere, generating intrafaujasite [H(4)Ru(4)(CO)(12)]. (c) Hexammineruthenium(III) complexes in Na(56)X and Na(56)Y underwent progressive thermal activation, in a CO and H(2) atmosphere. The generation process was considered to occur through conversion of the intermediates [Ru(NH(3))(5)(CO)](2+) and Ru(I)(CO)(3) to [Ru(6)(CO)(18)](2)(-). (d) A rapid (13)CO/(12)CO isotopic exchange was found to reversibly occur for [Ru(6)(CO)(18)](2)(-)/Na(56)X under H(2) coexistence. (e) Internal and external confinement of ruthenium carbonyl clusters were compared. (f) Oxidation fragmentation under an O(2) atmosphere and reductive regeneration under a CO and H(2) atmosphere were found to reversibly occur for [Ru(6)(CO)(18)](2)(-) guests. (g) Intrafaujasite anchoring of ruthenium carbonyl clusters showed a strong interaction with the extraframework Na(+) alpha-cage cations, through involvement of the oxygen end of the bridging or equatorial terminal carbonyl ligands.

Journal Article↗

Molecular motion in a spreading precursor film.

Spreading of a polymer drop on a solid substrate was monitored with molecular resolution. Three characteristic rates, i.e., the spreading rate of the precursor film D(spread)=(3.9+/-0.2)x10(3) nm(2)/s, the flow-induced diffusion rate of molecules within the film D(induced)=1.3+/-0.1 nm(2)/s, and the thermal diffusion coefficient of single molecules D(therm)</=0.10+/-0.03 nm(2)/s, were independently measured. Since D(spread)>>D(induced), the plug flow of polymer chains was identified as the main mass-transport mechanism of spreading with an insignificant contribution from the molecular diffusion.

Journal Article↗

The sodium currents of nerve under voltage clamp as heterogeneous kinetics. A model that is consistent with possible kinetic behavior.

A model is presented which explains in Na+ currents of voltage-clamped nerve as resulting from a heterogeneous initiation of a sequential kinetic process. This is in analogy with the heterogeneity of the kinetics of other dielectric relaxations. The results suggest that: (1) The kinetic processes responsible for the voltage response occur within the membrane rather than at the surface; (2) The heterogeneity is due to simultaneous thermal diffusion and electric field-induced charge migration: (3) The slow turnoff upon prolonged depolarization is a voltage-independent, thermally controlled process; (4) The fast turnoff upon instantaneous repolarization is the reverse of the turning-on process. All the kinetic parameters depend on the transmembrane potential in accord with the possible behavior expected from activated-state theory. The diffusion coefficient of the charged species in the membrane as found from the data agrees with that found by photobleaching experiments on general proteins in membranes. The charge on the molecule responsible for the heterogeneous "gating' can be calculated unambiguously from the data.

Electric Conductivity↗

Electrophoresis in the presence of gradients: I. Viscosity gradients.

In many cases, the resolution provided by capillary electrophoresis systems approaches that predicted for diffusion-limited separations. Once all device-related sources of band broadening have been eliminated or minimized, only thermal diffusion remains. In principle, peaks can be sharpened using gradients of various system characteristics such as gel concentration, buffer viscosity and electric field. However, it is not clear whether this can actually increase the resolution of the system. In this article, we focus our attention on viscosity gradients and we examine both continuous and step-like variations. Our results indicate that the performance of electrophoretic systems cannot be improved by viscosity gradients. They may provide extra stacking, and thus improve the resolution, when the injection width is non-negligible. However, for the systems considered here, the best resolution is obtained when the viscosity is uniform and the stacking is entirely performed at injection. We conclude by discussing the link between these results, the fundamental laws of thermodynamics, the nature of the detection process and the importance of having nonlinear effects in nonuniform systems.

Electrophoresis, Capillary↗

[Cerebral blood flow in subarachnoid hemorrhage: analysis in patients with poor outcomes].

Cerebral blood flow (CBF) of 6 patients with poor outcome after subarachnoid hemorrhage is analyzed. Neurological grades of these patients were grade III in 2 and grade IV in 4 patients, and subarachnoid hemorrhage on CT was diffuse and thick in all patients. Cerebral blood flow was continuously measured for 7 to 19 days by the thermal diffusion flow probe with a peltier stack which was left on the cerebral cortex at the surgery for ruptured aneurysm. Moreover, CBF studies by cold xenon CT and 133Xe inhalation methods were also performed in discussing cases. At the same time intracranial pressure was monitored. Cerebral angiography was carried out in all except for 2 patients who died due to severe cerebral vasospasm. The initial CBF value of all patients was 20 to 40 ml/100 g/min (mean value: 27 ml/100 g/min), and these were significantly low compared to normal value (50 ml/100 g/min). Moreover, these CBF was substantially decreased several days after surgery in all patients, and it was marked in 3 patients who died. From these results it was clear that the degree of vasospasm is important to determine the prognosis. One of 3 patients who died had ruptured left posterior cerebral artery aneurysm with occlusion of bilateral internal carotid arteries. In this case further decrease of CBF due to vasospasm was observed in addition to low initial CBF resulting diffuse low flow in both hemispheres although extracranial to intracranial bypass was performed. On the other hand, it was also shown that the intracranial pressure was an important factor to influence the outcomes.(ABSTRACT TRUNCATED AT 250 WORDS)

Aged↗

Measurement of the optical and thermal properties of biliary calculi using pulsed photothermal radiometry.

The optical absorption coefficients for biliary calculi are important in understanding the mechanism of laser-induced stone fragmentation. However, the heterogeneous composition of calculi and difficulties in producing optically thin samples prevent conventional spectrophotometric measurement techniques from being used. To overcome these limitations, we used a pulsed photothermal radiometry system to measure the optical absorption coefficients and thermal diffusivities of various biliary calculi. In the wavelength range examined (350-1,060 nm), there was strong optical absorption which was greater for pigment stones than for cholesterol stones. The data support the theory that the initiation of the plasma accompanying laser fragmentation of calculi is a thermal process.

Absorption↗

Anisotropic thermal conduction in a polymer liquid subjected to shear flow.

Flow-induced anisotropic thermal conduction in a polymer liquid is studied using force Rayleigh scattering. Time-dependent measurements of the complete thermal diffusivity tensor, which includes one off-diagonal and three diagonal components, are reported on an entangled polymer melt subjected to a uniform shear deformation. These data, in conjunction with mechanical measurements of the stress, provide the first direct evidence that the thermal conductivity tensor and the stress tensor are linearly related in a deformed polymer liquid.

Anisotropy↗

Water and hermal diffusivity in a lipid-water smectic phase.

We report the first application of light scattering to measurement of the hydrodynamic relaxation of inhomogeneities in water concentration within a multilamellar, or smectic A, phospholipid water system (dipalmitoyl) phosphatidyl choline). Although the relaxation process in the multilamellar phase is different from the diffusion process in liquid phases, the relaxation rate can be described in terms of a diffusion coefficient. For diffusion parallel to the lamellae, diffusion coefficients ranging from 8 x 10(-7) to 2 x 10(-5) cm2/s were measured over a range of temperature and water concentrations. We describe a model that expresses the diffusion coefficient in terms of the chemical potential for water inside the multilamellar phase and the effective thickness of a "free water zone." The deduced thickness of this free water zone is in good agreement with estimates from X-ray diffraction results. The activation energy for the diffusion process is also deduced from the data, and is found to decrease monotonically with increasing water concentration. We also found the thermal diffusivity to be about 10(-3) cm2/s with only a weak temperature and water concentration dependence. The experimental technique is a new version of forced Rayleigh scattering. The method uses the phase information of the scattered light to improve the ability to detect weak signals. Experimental details are reported.

Diffusion↗

Diffusion of asymmetric swimmers.

Particles moving along curved trajectories will diffuse if the curvature fluctuates sufficiently in either magnitude or orientation. We consider particles moving at a constant speed with either a fixed or a Gaussian distributed magnitude of curvature. At small speeds the diffusivity is independent of the speed. At larger particle speeds, the diffusivity depends on the speed through a novel exponent. We apply our results to intracellular transport of vesicles. In sharp contrast to thermal diffusion, the effective diffusivity increases with vesicle size and so may provide an effective means of intracellular transport.

Actins↗

Sensitivity analysis of one-dimensional heat transfer in tissue with temperature-dependent perfusion.

Design criteria for implantable heat-generating devices such as the total artificial heart require the determination of safe thresholds for chronic heating. This involves in-vivo experiments in which tissue temperature distributions are obtained in response to known heat sources. Prior to experimental studies, simulation using a mathematical model can help optimize the design of experiments. In this paper, a theoretical analysis of heat transfer is presented that describes the dynamic, one-dimensional distribution of temperature from a heated surface. Loss of heat by perfusion is represented by temperature-independent and temperature-dependent terms that can reflect changes in local control of blood flow. Model simulations using physiologically appropriate parameter values indicate that the temperature elevation profile caused by a heated surface adjacent to tissue may extend several centimeters into the tissue. Furthermore, sensitivity analysis indicates the conditions under which temperature profiles are sensitive to changes in thermal diffusivity and perfusion parameters. This information provides the basis for estimation of model parameters in different tissues and for prediction of the thermal responses of these tissues.

Body Temperature Regulation↗

Thermally induced nonlinear optical effects in an isotropic liquid crystal at 10.6 microm.

We investigate thermally induced nonlinear optical effects on a CO2 laser beam that passes through an isotropic liquid crystal film. We evaluate the thermal nonlinear coefficient of the refractive index at a wavelength of 10.6 microm by means of a thermographic technique combined with an optical method based upon the measurement of the self-defocusing effect caused by the heating of the liquid crystal induced by the laser beam. The novelty of our work is the application of thermography in order to measure the temperature field on the liquid crystal film caused by the partial absorption of the laser radiation by the liquid crystal. These measurements provide a precise evaluation of the thermal diffusion lengthof the liquid crystal under investigation. Moreover, thermography results in a straightforward experimental technique that can be used to investigate the thermal properties of a wide class of other fluids.

Journal Article↗

Thermodilution measurement of lung water.

The detection and measurement of pulmonary edema by the thermal-dye method appears to be accurate and reproducible under specified laboratory conditions. The ETV, which represents the difference in distribution volumes of the diffusible (thermal) indicator and the intravascular (green dye) indicator, should closely estimate the ELM (ETV = 0.984 ELM). Experimental measurements of ETV have shown a very good correlation with ELM, with a tendency for overestimation in normal lungs and underestimation in severely edematous lungs. In contrast to previous measurements using isotopic water methods, thermal-dye measurements have revealed that the estimation of ELM by ETV in severe edema (alveolar flooding) does not plateau. The limitations of the thermal-dye technique reflect the evenness of lung perfusion. Depending on their size and number, emboli produce perfusion defects and reduce ETV. Airway injury also reduces ETV, apparently by redistribution of blood flow. Alterations of ETV by hemodynamic factors suggest that reduction in perfusion pressure may be more significant than changes in flow, although more data are needed. Atelectasis without a reduction in blood flow does not decrease ETV. PEEP may increase ETV when lung injury is not uniform, perhaps by redistributing blood flow, and this maneuver may be useful in detecting underestimation of ELM. Position of the thermistor produces the greatest degree of variability by distorting the thermodilution curve and prolonging the MTT. This results in an increased ETV and an overestimation of ELM. In laboratory studies, the measurements of ETV can be validated by gravimetric analyses of lung water. Since this method of validation is not possible in clinical studies, measurements of ETV in patients must be interpreted in light of limitations demonstrated in the laboratory. Suggestions for avoiding the most common errors in measuring ETV are listed in Table 3.

Blood Pressure↗

Thermophoretic depletion follows Boltzmann distribution.

Thermophoresis, also termed thermal diffusion or the Soret effect, moves particles along temperature gradients. For particles in liquids, the effect lacks a theoretical explanation. We present experimental results at moderate thermal gradients: (i) Thermophoretic depletion of 200 nm polystyrene spheres in water follows an exponential distribution over 2 orders of magnitude in concentration; (ii) Soret coefficients scale linearly with the sphere's surface area. Based on the experiments, it is argued that local thermodynamic equilibrium is a good starting point to describe thermophoresis.

Diffusion↗

Multiexponential decay autocorrelation function in dynamic light scattering in near-critical ternary liquid mixture.

The dynamic structure factor of a ternary liquid mixture is calculated from the theory of thermodynamic fluctuations with the help of linearized hydrodynamic equations. The theoretical model allows evaluating and classifying the transport properties near a critical solution point of a ternary mixture. In the vicinity of the critical solution point, experimental dynamic light scattering measurements reveal two hydrodynamic relaxation modes with well-separated characteristic relaxation times. From the autocorrelation functions, we can determine two effective diffusivities D(1) and D(2). As theoretically predicted by a model developed in this work, one of these two modes can be associated with thermal diffusion and the other with mass diffusion. In the special case of an incompressible liquid mixture limit, D(1) and D(2) are decoupled, becoming thermodiffusion coefficient D(T) and mutual mass diffusion coefficient D(ij). A possible physical meaning of D(1) and D(2) for a ternary mixture is discussed.

Journal Article↗

Experimental evaluation of the thermal properties of two tissue equivalent phantom materials.

Tissue equivalent radio frequency (RF) phantoms provide a means for measuring the power deposition of various hyperthermia therapy applicators. Temperature measurements made in phantoms are used to verify the accuracy of various numerical approaches for computing the power and/or temperature distributions. For the numerical simulations to be accurate, the electrical and thermal properties of the materials that form the phantom should be accurately characterized. This paper reports on the experimentally measured thermal properties of two commonly used phantom materials, i.e. a rigid material with the electrical properties of human fat, and a low concentration polymer gel with the electrical properties of human muscle. Particularities of the two samples required the design of alternative measuring techniques for the specific heat and thermal conductivity. For the specific heat, a calorimeter method is used. For the thermal diffusivity, a method derived from the standard guarded comparative-longitudinal heat flow technique was used for both materials. For the 'muscle'-like material, the thermal conductivity, density and specific heat at constant pressure were measured as: k = 0.31 +/- 0.001 W(mK)(-1), p = 1026 +/- 7 kgm(-3), and c(p) = 4584 +/- 107 J(kgK)(-1). For the 'fat'-like material, the literature reports on the density and specific heat such that only the thermal conductivity was measured as k = 0.55 W(mK)(-1).

Evaluation Studies as Topic↗

Nonequilibrium thermodynamic description of the coupling between structural and entropic modes in supercooled liquids.

The density response of supercooled glycerol to an impulsive stimulated thermal grating (q=0.63 microm(-1)) has been studied in the temperature range (T=200-340 K) where the structure rearrangement (alpha relaxation) and the thermal diffusion occur on the same time scale. A strong interaction between the two modes occurs giving rise to a dip in the T dependence of the apparent thermal conductivity and a flattening of the apparent alpha-relaxation time upon cooling. A nonequilibrium thermodynamic model for the long time response has been developed. The model is capable to reproduce the experimental data and to explain the observed phenomenology.

Journal Article↗

A macroscopic description of biomolecular transport.

We present a general algorithm for computing the effective diffusion coefficient of a general class of biomolecular transport processes. The method can be applied to spatially discrete and continuous processes and takes into account the effects of thermal diffusion and chemical kinetics. To provide an illustration of the algorithm, the problem of protein translocation is considered.

Algorithms↗