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Analysis of diffusion delay in a layered medium. Application to heat measurements from muscle.

An analysis is presented of diffusional delays in one-dimensional heat flow through a medium consisting of several layers of different materials. The model specifically addresses the measurement of heat production by muscle, but diffusion of solute or conduction of charge through a layered medium will obey the same equations. The model consists of a semi-infinite medium, the muscle, in which heat production is spacially uniform but time varying. The heat diffuses through layers of solution and insulation to the center of the thermal element where heat flow is zero. Using Laplace transforms, transfer functions are derived for the temperature change in the center of the thermopile as a function of the temperature at any interface between differing materials or as a function of heat production in the muscle. From these transfer functions, approximate analytical expressions are derived for the time constants which scale the early and late changes in the central temperature. We find that the earliest temperature changes are limited by the diffusivities of the materials, whereas the approach to steady state depends on the total heat capacity of the system and the diffusivity of muscle. Hill (1937) analyzed a similar geometry by modeling the layered medium as a homogeneous system with an equivalent half thickness. We show that his analysis was accurate for the materials in his system. In general, however, and specifically with regard to modern thermopiles, a homogeneous approximation will lead to significant errors. We compare responses of different thermopiles to establish the limits of time resolution in muscle heat records and to correct them for diffusional delays. Using numerical techniques, we invert the Laplace transforms and show the time course of the temperature changes recorded by different instruments in response to different patterns of heat production.

Animals↗

Preparation of an effective light-cured bonding agent for orthodontic application.

OBJECTIVE: The purpose of this study was to prepare a light-cured adhesive applicable for orthodontics by mixing monomers and a polymerized reactive organic composite filler (prepolymerized trimethylolpropane trimethacrylate-filler, TMPT-filler). METHODS: The monomer component was a mixture of 3.0 wt% 2-hydroxy-3-(2-naphthoxy)propyl methacrylate (HNPM) in triethylene glycol dimethacrylate. This was applied to extracted bovine tooth enamel after acid etching with 65 wt% phosphoric acid for 30 s. After 24 h in 37 degrees C water, the tensile bond strength was measured, and the data were analyzed with Duncan's new multiple range test (p < 0.01 or 0.05). RESULTS: The tensile bonding strength to enamel etched with 65 wt% phosphoric acid was 13.1 +/- 0.5 MPa, and the thermal stability of the bond was excellent. SEM examination of the cross-sectioned specimens modified with HCl demineralization showed that when the diffusion time prior to light irradiation was only 1 min, a well-developed resin honeycomb-like structure was created in the enamel surface in the formulation containing HNPM. SIGNIFICANCE: Monomer impregnation beyond the etched enamel surface was important for resin-enamel bonding, increasing bonding strength and thermal stability. HNPM was effective in enhancing monomer diffusion and impregnation of the etched enamel surface.

Acrylates↗

Interpretation of apparent activation energies for electron transport in dye-sensitized nanocrystalline solar cells.

Electron transport in dye-sensitized nanocrystalline solar cells appears to be a slow diffusion-controlled process. Values of the apparent electron diffusion coefficient are many orders of magnitude smaller than those reported for bulk anatase. The slow transport of electrons has been attributed to multiple trapping (MT) at energy levels distributed exponentially in the band gap of the nanocrystalline oxide. In the MT model, release of immobile electrons from occupied traps to the conduction band is a thermally activated process, and it might therefore be expected that the apparent electron diffusion coefficient should depend strongly on temperature. In fact, rather small activation energies (0.1-0.25 eV) have been derived from time and frequency resolved measurements of the short circuit photocurrent. It is shown that the MT model can give rise to such anomalously low apparent activation energies as a consequence of the boundary conditions imposed by the short circuit condition and the quasi-static relationship between changes in the densities of free and trapped electrons. This conclusion has been confirmed by exact numerical solutions of the time-dependent generation/collection problem for periodic excitation that provide a good fit to experimental data.

Letter↗

Thermal lens spectrometry in aqueous solutions of Brij 35: investigation of micelle effects on the time-resolved and steady-state signals.

This work investigates the effect of micelles on the time-resolved and steady-state thermal lens signals in aqueous solutions. The temperature gradient produced subsequently to non-radiative relaxation of the sample induces migration of micelles towards the colder region of the irradiated area along with an opposite flow of solute molecules. This phenomenon, known as the Soret effect, produces an additional probe beam signal with a rise time that is much longer than the thermal time constant and depends on the surfactant and solute concentrations. Extrapolation of the mass-diffusion constant at zero solute concentration allowed the determination of diffusion coefficients that are close to those derived by other methods for Brij 35 micelles in water. It is also shown that the surfactant has only a small effect on the thermal lens signal and that the enhancement produced by micelles with respect to pure water originates mainly firom the Soret effect. It follows that interpretation of experimental data without discriminating both components of the probe beam signal can lead to erroneous values of dn/dT.

Detergents↗

Dynamic system for the calibration of semi-volatile carbonyl compounds in air.

A dynamic calibration system designed for generating accurate and precise concentrations of semi-volatile carbonyls in the ppb (v/v) (ppbv)-ppt (v/v) (pptv) range has been developed and tested. Alkanals from C6 to C9 were used as test compounds. Diffusion rates of their vapours from capillary tubes were determined theoretically and with two methods whose accuracy was independently evaluated with liquid standard solutions. Methods selected for testing the calibration system were those commonly used for the selective quantification of carbonyls in air. One is based on the well-known reaction with 2,4-dinitrophenylhydrazine (DNPH), followed by the analysis of formed hydrazones by HPLC-UV. The other is based on the retention of carbonyls on graphitic carbon adsorbents, followed by MS detection of the sample injected into a capillary column by thermal desorption. A good consistency was found between the values of the diffusion rates determined by the two methods. The scatter between the two methods was in the range of +/-10% when diffusion rates of ca. 1 ng/s were attained. Experimental values closely approached those calculated by applying the equation describing the diffusion of a vapour in equilibrium with the liquid through a capillary tube.

Air↗

Variable-density groundwater flow and solute transport in heterogeneous porous media: approaches, resolutions and future challenges.

In certain hydrogeological situations, fluid density variations occur because of changes in the solute or colloidal concentration, temperature, and pressure of the groundwater. These include seawater intrusion, high-level radioactive waste disposal, groundwater contamination, and geothermal energy production. When the density of the invading fluid is greater than that of the ambient one, density-driven free convection can lead to transport of heat and solutes over larger spatial scales and significantly shorter time scales than compared with diffusion alone. Beginning with the work of Lord Rayleigh in 1916, thermal and solute instabilities in homogeneous media have been studied in detail for almost a century. Recently, these theoretical and experimental studies have been applied in the study of groundwater phenomena, where the assumptions of homogeneity and isotropy rarely, if ever, apply. The critical role that heterogeneity plays in the onset as well as the growth and/or decay of convective motion is discussed by way of a review of pertinent literature and numerical simulations performed using a variable-density flow and solute transport numerical code. Different styles of heterogeneity are considered and range from continuously "trending" heterogeneity (sinusoidal and stochastic permeability distributions) to discretely fractured geologic media. Results indicate that both the onset of instabilities and their subsequent growth and decay are intimately related to the structure and variance of the permeability field. While disordered heterogeneity tends to dissipate convection through dispersive mixing, an ordered heterogeneity (e.g., sets of vertical fractures) allows instabilities to propagate at modest combinations of fracture aperture and separation distances. Despite a clearer understanding of the processes that control the onset and propagation of instabilities, resultant plume patterns and their migration rates and pathways do not appear amenable to prediction at present. The classical Rayleigh number used to predict the occurrence of instabilities fails, in most cases, when heterogeneous conditions prevail. The incorporation of key characteristics of the heterogeneous permeability field into relevant stability criteria and numerical models remains a challenge for future research.

Chemical Phenomena↗

Dynamic simulations of membranes with cytoskeletal interactions.

We describe a simulation algorithm for the dynamics of elastic membrane sheets over long length and time scales. Our model includes implicit hydrodynamic coupling between membrane and surrounding solvent and allows for arbitrary external forces acting on the membrane surface. In particular, the methodology is well suited to studying membranes in interaction with cytoskeletal filaments. We present results for the thermal undulations of a lipid bilayer attached to a regular network of spectrin filaments as a model for the red blood cell membrane. The dynamic fluctuations of the bilayer over the spectrin network are quantified and used to predict the macroscopic diffusion constant of band 3 on the surface of the red blood cell. We find that thermal undulations likely play a role in the mobility of band 3 in the plane of the erythrocyte membrane.

Algorithms↗

Hydrolytic degradation and morphologic study of poly-p-dioxanone.

The in vitro hydrolytic degradation of 2-0 size PDS monofilament suture was studied for the purpose of revealing its morphologic structure and degradation mechanism. The sutures were immersed in phosphate buffer of pH 7.44 for up to 120 days at 37 degrees C. These hydrolyzed sutures were examined by the changes in tensile properties, weight, thermal properties, x-ray diffraction structure, surface morphology, and dye diffusion phenomena. It was found that hydrolysis had significant effects on the change of PDS fiber morphology and properties. Hydrolysis, however, had no significant effect on overall molecular orientation of the fiber until the very late stage. PDS suture fibers retained their skeleton throughout the earlier periods of hydrolysis concurrent with mass and tensile strength losses. PDS sutures exhibited an absorption delay of 120 days. Both heat of fusion and melting point exhibited a maximum function of hydrolysis time. Hydrolysis of PDS suture fibers proceeded through two stages: random scission of chain segments located in the amorphous regions of microfibrils and intermicrofibrillar space, followed by stepwise scission of chain segments located in the crystalline regions of microfibrils. Dye diffusion data showed that the passage along the longitudinal direction of the fiber was relatively easier than the lateral direction as evident in the diffusion coefficient, activation energy, and flexibility of chain segments. Swiss-cheese model of fiber structure appears to describe the observed dye diffusion phenomena and their dependence on hydrolysis time and dying temperature.

Adsorption↗

Effects of crystalline microstructure on drug release behavior of poly(epsilon-caprolactone) microspheres.

This study investigates the release behavior of papaverine from poly(epsilon-caprolactone) (PCL) microparticles prepared by the oil/water solvent evaporation method. Microparticles were characterized in terms of crystalline morphology, size, drug loading, and encapsulation efficiency by using differential scanning calorimetry (DSC), small angle X-ray scattering (SAXS), scanning electron microscopy (SEM), and UV spectrometry. The release behavior of papaverine was governed by the microstructure of PCL microparticles, suggesting that the environment for diffusion changes according to processing conditions such as polymer solution concentration, thermal history, and polymer molecular weight. As the PCL solution concentration increased, the drug release behavior showed a more sustained pattern. This result indicates that the size of the PCL microparticles is a determining factor for drug release. And when higher PCL molecular weight is used for preparation of microparticles, it led to a rapid release. Furthermore, a more delayed pattern of drug release profile was obtained in the sample prepared with higher thermal treatment. These results suggest that the crystalline microstructure of PCL microparticles plays an important role in its drug release behavior.

Calorimetry, Differential Scanning↗

Cocrystallization model for synthetic biodegradable poly(butylene adipate-co-butylene terephthalate).

Synthetic biodegradable poly(butylene adipate-co-butylene terephthalate), P(BA-co-BT), with 56 mol % butylene adipate, BA, was characterized by solid-state NMR spectroscopy, thermal analysis, X-ray diffraction, computer modeling, and polarization microscopy. The NMR study showed the presence of BA and butylene terephthalate, BT. T(1C) NMR measurements proved that some BA and BT units were in crystalline regions. Thermal analysis showed one glass-transition temperature and a single diffuse melting endotherm corresponding to a large melting-point depression of about 100 degrees C compared with poly(butylene terephthalate), PBT. These results suggest that there is only one crystalline phase. An X-ray fiber diagram of a stretched film could be indexed with the same unit cell as that for PBT. Computer modeling showed that the adipate unit fits into the crystal structure of PBT by adopting a TTGTG dihedral angle sequence in the crystalline conformation proposed for the cocrystallization model. The predicted fiber diagram from the proposed model qualitatively agrees with the experimental one. Polarization microscopy revealed that the spherulite growth rate of P(BA-co-BT) was similar to that for poly(butylene adipate), PBA.

Absorbable Implants↗

Structural modulation of molybdenyl iodate architectures by alkali metal cations in AMoO3(IO3) (A = K, Rb, Cs): a facile route to new polar materials with large SHG responses.

Three new molybdenyl iodates, KMoO3(IO3) (1), RbMoO3(IO3) (2), and CsMoO3(IO3) (3), have been prepared through the hydrothermal reactions of MoO3 with AIO4 (A = K, Rb, or Cs) at 180 C. These compounds are isolated as nearly colorless, air-stable crystals. Single-crystal X-ray diffraction experiments reveal that 1 possesses a corrugated layered structure constructed from molybdenum oxide chains that are bridged by iodate anions. The puckering of the layers is caused by the alignment of bent molybdenyl (MoO2(2+)) groups along one side of the molybdenum oxide chains. The K+ cations separate these layers from one another and serve to balance charge. In contrast, compounds 2 and 3, which are isostructural, form three-dimensional structures with small cavities filled with Rb+ or Cs+ cations. The differences between the structures of 1 and those of 2 and 3 are due to rotation of the molybdenyl units as translation occurs down the molybdenum oxide chains in order to accommodate the increased size of the Rb+ and Cs+ cations. This rotation allows for the iodate anions to bridge the molybdenum oxide chains in an additional dimension, creating a three-dimensional network structure. Furthermore, while 1 crystallizes in a centrosymmetric space group, 2 and 3 crystallize in polar space groups. Second-harmonic generation measurements on 2 and 3 show large responses of 400x alpha-quartz. Differential scanning calorimetry measurements demonstrate that 2 and 3 are thermally stable to 494 and 486 C, respectively. UV-vis diffuse reflectance spectra of these compounds show a high degree of transparency from 1 to 3 eV and a band gap of 3.1 eV.

Journal Article↗

A comparison of the response to hyperthermia of murine haemopoietic stem cells (CFU-S) and L1210 leukaemia cells: enhanced killing of leukaemic cells in presence of normal marrow cells.

When the clonogenic survival of mouse haemopoietic stem cells (CFU-S) and leukaemia L1210 cells growth as ascites tumours are compared after being heated in vitro and assayed in vivo by spleen-colony assay, there is no significant difference in the terminal slopes of the survival curves. The shoulders of the survival curves differ, but this may be explained by differences in cell kinetics. By contrast, L1210 leukaemic marrow cells are considerably more susceptible to the lethal effects of hyperthermia (43 degrees C) than either normal marrow stem cells or L1210 leukaemic cells grown as ascites tumours. Moreover, the killing of L1210 ascites cells by hyperthermia can be enhanced by heating L1210 ascites cells with an equal number of normal marrow cells, or as upernatant removed from heated marrow cells. Most cells in lukaemic marrow are normal, and it is postulated that the increased thermal sensitivity of L1210 cells in leukaemic marrow is caused by diffusible factors (e.g. lysosomal enzymes) released by heating normal marrow cells.

Animals↗

Determination of central blood volume and extravascular lung water.

UNLABELLED: In patients undergoing thoracic surgery central blood volume is subject to large variations and extravascular lung water may change critically due to fluid shifts. Therefore, an accurate monitoring of these parameters, in particular under perioperative conditions, seems to be desirable. This study describes an improved method for the measurement of intrathoracic volumes. Experiments were carried our in 9 mongrel dogs under piritramide-N2O anesthesia. In order to produce low cardiac output in combination with uneven distribution of perfusion, measurements were performed under base line conditions and after postural changes. Indicators (cold and indocyanine green dye) were injected into the v. cava and indicator kinetics were recorded from the pulmonary artery and aorta using thermistor-fiberoptic catheters. The transport functions of cold and dye were computed from the corresponding pairs of dilution curves. From the transport functions, the mean transit times of the intravascular (dye) and diffusible (cold) indicator were determined. Central blood volume and extravascular lung thermal volume were calculated from the mean transit times and a thermodilution cardiac output. RESULTS: Under base line conditions, central blood volume was 15.3 +/- 2.5 ml/kg body weight. In orthostasis, a significant and reversible reduction to 11.6 +/- 2.4 ml/kg body weight was found. Cardiac output fell significantly from 3.3 +/- 0.5 to 2.4 +/- 1.1. l/min. In contrast, the slight decrease of extravascular lung thermal volume was not statistically significant. It is concluded that the method presented is sensitive enough to detect even small changes of central blood volume.(ABSTRACT TRUNCATED AT 250 WORDS)

Animals↗

Fluctuations of temperature gradients in turbulent thermal convection.

Broad theoretical arguments are proposed to show, formally, that the magnitude G of the temperature gradients in turbulent thermal convection at high Rayleigh numbers obeys the same advection-diffusion equation that governs the temperature fluctuation T , except that the velocity field in the new equation is substantially smoothed. This smoothed field leads to a -1 scaling of the spectrum of G in the same range of scales for which the spectral exponent of T lies between -7/5 and -5/3 . This result is confirmed by measurements in a confined container with cryogenic helium gas as the working fluid for Rayleigh number Ra=1.5x 10(11) . Also confirmed is the logarithmic form of the autocorrelation function of G . The anomalous scaling of dissipation-like quantities of T and G are identical in the inertial range, showing that the analogy between the two fields is quite deep.

Journal Article↗

Thermodynamic suppression of Brownian motion.

We have used helium-3 nuclear reaction analysis to measure the Brownian motion (intradiffusion coefficient) of polystyrene in a partially miscible blend with poly(alpha-methylstyrene). In the one-phase region, when the correlation length is close to the polystyrene chain size, the intradiffusion coefficient falls to half of its thermal value. For larger and smaller values of the correlation length, diffusion is normal. These results show that the correlation length of a polymer blend constrains polymer diffusion, as suggested from previous neutron scattering measurements, and mean-field theory.

Journal Article↗

Thermal dye double indicator dilution measurement of lung water in man: comparison with gravimetric measurements.

The thermal dye double indicator dilution technique for estimating lung water was compared with gravimetric analyses in nine human subjects who were organ donors. As observed in animal studies, the thermal dye measurement of extravascular thermal volume (EVTV) consistently overestimated gravimetric extravascular lung water (EVLW), the mean (SEM) difference being 3.43 (0.59) ml/kg. In eight of the nine subjects the EVTV -3.43 ml/kg would yield an estimate of EVLW that would be from 3.23 ml/kg under to 3.37 ml/kg over the actual value EVLW at the 95% confidence limits. Reproducibility, assessed with the standard error of the mean percentage, suggested that a 15% change in EVTV can be reliably detected with repeated measurements. One subject was excluded from analysis because the EVTV measurement grossly underestimated its actual EVLW. This error was associated with regional injury observed on gross examination of the lung. Experimental and clinical evidence suggest that the thermal dye measurement provides a reliable estimate of lung water in diffuse pulmonary oedema states.

Adolescent↗

Comparison of titanium-tantalum and titanium-niobium alloys for application as dental implants.

For the diffusion bonding of Ti alloys to alumina, materials with a similar thermal expansion coefficient to alumina are required. Such materials were developed by alloying the biocompatible elements Ta and Nb to titanium (Ti-Ta30 and Ti-Ta40, Ti-Nb40 and Ti-Nb50). While measuring the corrosion behavior of these alloys in 0.9% saline solution, no difference could be observed. The Ti-Ta alloys are superior in their mechanical properties to Ti-Nb alloys.

Biocompatible Materials↗