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Ion conduction mechanisms and thermal properties of hydrated and anhydrous phosphoric acids studied with 1H, 2H, and 31P NMR.

To understand the behaviors of phosphoric acids in fuel cells, the ion conduction mechanisms of phosphoric acids in condensed states without free water and in a monomer state with water were studied by measuring the ionic conductivity (sigma) using AC impedance, thermal properties, and self-diffusion coefficients (D) and spin-lattice relaxation times (T1) with multinuclear NMR. The self-diffusion coefficient of the protons (H+ or H3O+), H2O, and H located around the phosphate were always larger than the diffusion coefficients of the phosphates and the disparity increased with increasing phosphate concentration. The diffusion coefficients of the samples containing D2O paralleled those in the protonated samples. Since the 1H NMR T1 values exhibited a minimum with temperature, it was possible to determine the correlation times and they were found to be of nanosecond order for a distance of nanometer order for a flip. The agreement of the ionic conductivities measured directly and those calculated from the diffusion coefficients indicates that the ion conduction obeys the Nernst-Einstein equation in the condensed phosphoric acids. The proton diffusion plays a dominant role in the ion conduction, especially in the condensed phosphoric acids.

Journal Article↗

Biomolecular hydration: from water dynamics to hydrodynamics.

Thermally driven rotational and translational diffusion of proteins and other biomolecules is governed by frictional coupling to their solvent environment. Prediction of this coupling from biomolecular structures is a longstanding biophysical problem, which cannot be solved without knowledge of water dynamics in an interfacial region comparable to the dry protein in volume. Efficient algorithms have been developed for solving the hydrodynamic equations of motion for atomic-resolution biomolecular models, but experimental diffusion coefficients can be reproduced only by postulating hundreds of rigidly bound water molecules. This static picture of biomolecular hydration is fundamentally inconsistent with magnetic relaxation dispersion experiments and molecular dynamics simulations, which both reveal a highly dynamic interface where rotation and exchange of nearly all water molecules are several orders of magnitude faster than biomolecular diffusion. Here, we resolve this paradox by means of a dynamic hydration model that explicitly links protein hydrodynamics to hydration dynamics. With the aid of this model, bona fide structure-based predictions of global biomolecular dynamics become possible, as demonstrated here for a set of 16 proteins for which accurate experimental rotational diffusion coefficients are available.

Animals↗

Thermal depolarization of fluorescence from polytene chromosomes stained with acridine orange.

The degree of polarization of fluorescence from stretched Chironomus thummi polytene chromosomes, stained with low concentrations of acridine orange (AO), decreases with increasing temperature. The "half temperature" of this decrease (T((1/2)R)) is lower than the expected DNA thermal denaturation temperature (T(m)) by about 20 degrees C. T((1/2)R) is lowered as histone is removed from chromosomes. Balbiani ring regions of the fourth chromosome have T((1/2)R)'s much lower than other regions, and nearly as low as chromosomes which had been extensively pretreated with trypsin to remove histone and other proteins. Measurements of the thermal change in the rotational diffusion rate of AO in solution with DNA indicate that the temperature at which the DNA-AO bonding changes from a "rigid" to a "loose" mode varies with the GC percentage of the DNA, and in the same fashion as T(m), although 20 degrees C lower.

Acridines↗

Mitigating thermal mechanical damage potential during two-photon dermal imaging.

Two-photon excitation fluorescence microscopy allows in vivo high-resolution imaging of human skin structure and biochemistry with a penetration depth over 100 microm. The major damage mechanism during two-photon skin imaging is associated with the formation of cavitation at the epidermal-dermal junction, which results in thermal mechanical damage of the tissue. In this report, we verify that this damage mechanism is of thermal origin and is associated with one-photon absorption of infrared excitation light by melanin granules present in the epidermal-dermal junction. The thermal mechanical damage threshold for selected Caucasian skin specimens from a skin bank as a function of laser pulse energy and repetition rate has been determined. The experimentally established thermal mechanical damage threshold is consistent with a simple heat diffusion model for skin under femtosecond pulse laser illumination. Minimizing thermal mechanical damage is vital for the potential use of two-photon imaging in noninvasive optical biopsy of human skin in vivo. We describe a technique to mitigate specimen thermal mechanical damage based on the use of a laser pulse picker that reduces the laser repetition rate by selecting a fraction of pulses from a laser pulse train. Since the laser pulse picker decreases laser average power while maintaining laser pulse peak power, thermal mechanical damage can be minimized while two-photon fluorescence excitation efficiency is maximized.

Burns↗

A diffusive badge sampler for volatile organic compounds in ambient air and determination using a thermal desorption-GC/MS system.

A sensitive personal badge sampler packed with Carbopack B for ambient levels of volatile organic compounds and an analytical system using a thermal desorption-preconcentration-GC/MS have been developed. The capacity of the new sampler was sufficient for an 8-h sampling period, and the analytical method was sensitive enough for the measurement of sub-ppb levels for a 2-h sampling period. The samplers were compared to diffusive samplers (OVM 3500) for typical environmental concentrations. There was a good correlation between the results obtained with the new samplers and the OVM samplers.

Air Pollutants, Occupational↗

[Post mortem diffusion of carbon monoxide to muscles and blood--preliminary examinations].

The purpose of the study was to determine whether the postmortem diffusion of carbon monoxide (CO) significantly affected the results of carboxyhemoglobin (COHb) and carboxymyoglobin (COMb) determinations. The musculocutaneous and muscular specimens collected from adult cadavers were used. The specimens were treated with CO for 24 h at room temperature. COHb and COMb were determined using gas chromatography. It was demonstrated that the skin substantially limited the diffusion of CO which slightly penetrated only the superficial layers of the muscle and did not change the blood level of COHb in the 4.5-cm layer of the muscle located underneath. The CO diffusion through the superficially charred and thermally coagulated muscle did not differ from that observed in the intact integuments. On the other hand, the membrane of the skin completely deprived of the adipose layer was not the barrier to moderate diffusion into the blood layer situated below. Thus, in charred corpses the results pf COHb and COMb determinations in the material collected under the layer of charred and coagulated tissues enable us to determine whether the victim was alive at the moment of the outbreak.

Adult↗

Temperature affects the diffusion of small molecules through cytosol of fish muscle.

Undiluted cytosolic extracts were prepared from fast glycolytic muscle tissue of white perch (Morone americanus). Diffusion coefficients (D) through the cytosol preparations were estimated in vitro for a series of selected low molecular weight compounds using an experimental diffusion chamber. Determinations were made at 5 degrees and 25 degrees C to assess thermal sensitivity of the process. Non-metabolizable analogues of naturally occurring compounds were employed to avoid chemical alteration of solutes by the catalytically competent preparations during diffusion experiments. Kinematic viscosity of cytosolic extracts, which is a major determinant of diffusive resistance, increases from 2.94 +/- 0.06 to 5.35 +/- 0.02 X 10(-2) cm2 s-1 between temperatures of 25 degrees and 5 degrees C (Q10 = 1.35 +/- 0.01). The diffusion coefficients (D) of D-lactic acid are 2.26 +/- 0.84 and 0.79 +/- 0.15 X 10(-6) cm2s-1 at 25 degrees and 5 degrees C, respectively (Q10 = 1.84 +/- 0.36). The D values of 2-deoxyglucose are 2.87 +/- 1.01 and 1.22 +/- 0.36 X 10(-6) cm2s-1 at 25 degrees and 5 degrees C (Q10 = 1.75 +/- 0.54). The D values of Ca2+ are 2.47 +/- 0.28 and 1.09 +/- 0.36 X 10(-6) cm2s-1 at 25 degrees and 5 degrees C (Q10 = 2.04 +/- 0.36). The D values for the ATP analogue, AMP-PNP, are 0.87 +/- 0.33 and 0.81 +/- 0.15 X 10(-6) cm2s-1 at 25 degrees and 5 degrees C (Q10 = 0.98 +/- 0.12). AMP-PNP is the only compound tested which did not show significant thermal sensitivity of diffusion. Recently reported changes in muscle cell ultrastructure induced by temperature acclimation of fishes may serve to counteract the effect of temperature change on diffusion of key small molecules through the aqueous cytoplasm, thus maintaining flux rates between cellular compartments. These mechanisms may be of considerable import in achieving relative temperature independence of cellular function that is characteristic of many eurythermal aquatic animals.

Adenosine Triphosphate↗

Validation of intermolecular pair potential model of SiH4: molecular-dynamics simulation for saturated liquid density and thermal transport properties.

We demonstrate a validation of the intermolecular pair potential model of SiH(4), which is constructed from ab initio molecular-orbital calculations and expressed as the sum of the exponential and the London dispersion terms. The saturated liquid densities of SiH(4) are calculated for temperatures from 100 to 225 K by molecular-dynamics (MD) simulation. The average deviation between the experiment and the MD simulation using the present potential model is 3.9%, while the deviations exceed 10% for other well-known potential models such as the five-center Lennard-Jones (LJ) model. Subsequently, the shear viscosity, the thermal conductivity, and the self-diffusion coefficient of liquid SiH(4) are calculated by an equilibrium MD simulation with the Green-Kubo formula from 100 to 225 K. The average deviations from experiment are 11.8% and 13.7% for the shear viscosity and the thermal conductivity, respectively. Comparing the present model with an empirical one-center LJ model, it turns out that the rotational energy transfer through the intermolecular potential energy, which comes from the anisotropic potential energy, plays an important role in the thermal conductivity of liquid SiH(4). These results indicate that the present intermolecular potential model has an ability to give realistic pictures for liquid SiH(4) through molecular simulations.

Journal Article↗

Propranolol hydrochloride release behaviour of crosslinked chitosan membranes.

Chitosan membranes of 20 microns thickness were prepared by a solvent evaporation technique and crosslinked with different concentrations of glutaraldehyde to obtain membranes of various degrees of crosslinking. These membranes were characterized by thermogravimetric (TG) analysis, differential scanning calorimetry (DSC) and tensile strength studies. The effect of crosslinking on the permeability of membranes to propranolol hydrochloride was evaluated by permeation studies conducted in static glass diffusion cells. A decrease in the thermal stability of chitosan membranes due to crosslinking was observed. The tensile strength of the membranes was improved by crosslinking. The introduction of crosslink points within the membrane reduced its permeability to propranolol hydrochloride as evidenced by decreased permeability and diffusion coefficients. Permeability studies revealed the operation of a pore mechanism in the transport of hydrophilic agents such as propranolol hydrochloride through chitosan and crosslinked chitosan membranes.

Calorimetry, Differential Scanning↗

The cavity sealing ability of composite restorations subjected to thermal stress.

An artificial caries technique, using a diffusion controlled acidified gel, was used to create in vitro artificial lesions adjacent to composite restorations. Prior to gel immersion, test specimens were temperature-cycled in a machine designed specifically for this purpose. Examination of control specimens showed little evidence of leakage, the presence of a cavity wall lesion being used as an indication of leakage. Compared to the controls, the test specimens showed either a reduction or no change in leakage pattern. It is suggested that thermal percolation may not be of clinical significance in relation to composite restorations.

Absorption↗

Thermal physics in carbon nanotube growth kinetics.

The growth of single wall carbon nanotubes (SWNTs) mediated by metal nanoparticles is considered within (i) the surface diffusion growth kinetics model coupled with (ii) a thermal model taking into account heat release of carbon adsorption-desorption on nanotube surface and carbon incorporation into the nanotube wall and (iii) carbon nanotube-inert gas collisional heat exchange. Numerical simulations performed together with analytical estimates reveal various temperature regimes occurring during SWNT growth. During the initial stage, which is characterized by SWNT lengths that are shorter than the surface diffusion length of carbon atoms adsorbed on the SWNT wall, the SWNT temperature remains constant and is significantly higher than that of the ambient gas. After this stage the SWNT temperature decreases towards that of gas and becomes nonuniformly distributed over the length of the SWNT. The rate of SWNT cooling depends on the SWNT-gas collisional energy transfer that, from molecular dynamics simulations, is seen to be efficient only in the SWNT radial direction. The decreasing SWNT temperature may lead to solidification of the catalytic metal nanoparticle terminating SWNT growth or triggering nucleation of a new carbon layer and growth of multiwall carbon nanotubes.

Journal Article↗

Thermal-field propagation in an exocontact zone of a magmatic body and its impact on radiogenic isotope concentrations in minerals.

In application of radioactive isotope systems (K-Ar, Rb-Sr etc.) during the last decades, experience was gained not only on their geochronometrical uses, but also on estimations of some important parameters of geological processes, especially temperatures and durations of superimposed thermal events. In this paper, the formation of an exocontact thermal field of a magmatic intrusion is considered as a spreading of a thermal source delta-function. Appropriate solutions of the heat-transfer equation are deduced and correlated with diffusion parameters of the radiogenic argon, coupling radioactive, thermal and kinetic parameters in an exocontant zone of a magmatic body. These solutions were used for quantitative reinterpretations of data taken from Hart's classical paper [The petrology and isotopic mineral age relations of a contact zone in the Front Range, Colorado. J. Geol., 1964, v. 72, pp. 493-525]. Theoretic and measured radiogenic argon and strontium concentrations within exocontact aureoles are found to be in good concordance.

Geological Phenomena↗

Overdamped sine-Gordon kink in a thermal bath.

We study sine-Gordon kink diffusion at finite temperature in the overdamped limit. By means of a general perturbative approach, we calculate the first- and second-order (in temperature) contributions to the diffusion coefficient. We compare our analytical predictions with numerical simulations. The good agreement allows us to conclude that, up to temperatures where kink-antikink nucleation processes cannot be neglected, a diffusion constant linear and quadratic in temperature gives a very accurate description of the diffusive motion of the kink. The quadratic temperature dependence is shown to stem from the interaction with the phonons. In addition, we calculate and compute the average value < phi(x,t)> of the wave function as a function of time, and show that its width grows with square root of t. We discuss the interpretation of this finding and show that it arises from the dispersion of the kink center positions of individual realizations which all keep their width.

Journal Article↗

Proposed methods for the measurement of regional renal blood flow using heat transfer analysis.

The kidney, with its heterogeneous regional perfusion in the two anatomically and functionally distinct vascular beds of the renal cortex and medulla, and with its non-uniform blood vessel geometries, presents a unique challenge for measuring intrarenal blood flow distribution. Determining whole organ perfusion, on the other hand, is comparatively simple for the kidney, but it provides relatively little information about the suspected dependency of renal excretory function on local perfusion rate. Among the variety of methods proposed for gauging regional renal blood flow, some depend on measuring one or more of the tissue's thermal properties. The most straightforward, but least reliable, involve measurements either of focal tissue temperature alone, or of regional tissue thermal gradients. Simply using heat as a diffusible indicator, however, is unreliable as a measure of blood flow, for many of the same reasons that using an inert gas in a dilution technique is unreliable. Recently developed thermal analytical methods, though, hold promise for measuring local tissue blood flow with accuracy and precision. Two of them are reviewed here. One depends on measurement of the effective thermal conductivity of a small mass of tissue by evaluating the steady state ratio between regional unidirectional heat flux across it and the associated temperature gradient in one vector along a segment of it through an imposed spheroidal heat field. The other depends on analyses of tissue temperature decay subsequent to a controlled pulse of heat delivered through a small inserted thermistor bead. Both techniques use bioheat transfer equations to deduce regional blood flow by differentiating between heat dissipation due to local thermal conductivity and that attributable to the effects of regional convection. Although both methods are unavoidably invasive, neither produces debilitating damage in the tissue volume in which perfusion is measured, nor increases local temperature or metabolism enough to affect blood flow itself. Both techniques quantify local blood flow in small volumes of tissue by detailed evaluation of the many properties of tissue and blood which affect heat transfer, and both allow for a virtually unlimited number of nearly continuous sequential measurements at short (nom. 1 min) time intervals.

Animals↗

Themodynamic and transport properties of intermediate states of the photocyclic reaction of photoactive yellow protein.

Themodynamic and transport properties of intermediate states of the photocyclic reaction of photoactive yellow protein (PYP) were studied by a combination of the pulsed laser-induced transient grating (TG), transient lens (TrL), and photoacoustic (PA) spectroscopies from tens of nanoseconds to hundreds of milliseconds. The diffusion coefficients (D) of PYP in the ground state (pG) and of the second intermediate state (pB) were determined by the TG analysis, and it was found that D of pG is about 1.2 times larger than D of pB. At the same time, D at various denatured conditions were measured using guanidine hydrochloride as the denaturant. D of completely unfolded protein is about 0.4 times that of the native form. The enthalpy of pB is estimated to be 60 kJ/mol by the TrL method with an assumption that the volume change of pB is not sensitive to the temperature. Since the enthalpy of the first intermediate state (pR) is as high as 160 kJ/mol, it implies that most of the photon energy is stored as the strain of the protein in pR, and this may be the driving force for the successive reaction to pB. From the temperature dependence of the volume change, the difference in the thermal expansion coefficients between pG and pR was calculated. All of the characteristic features of PYP, the negative volume change, the larger thermal expansion coefficient, and the slower diffusion process, indicate that the intermediate pR and pB are reasonably interpreted in terms of the unfolded (loosened) protein structure.

Bacterial Proteins↗

Spatially patterned static roughness superimposed on thermal roughness in a condensed phospholipid monolayer

Imaging of diffuse light scattering in reflection from a phospholipid monolayer at the air/water interface has revealed a previously undetected separation of the monolayer into two regions distinguishable by the intensity of their scattering. In monolayers of L-dipalmitoyl phosphatidylcholine in the condensed phase, chiral-shaped domains are surrounded by a brighter region that covers approximately half the monolayer. While the scattered intensity from both regions increases with surface pressure in a manner consistent with scattering from thermally induced capillary waves, the additional scattering from the brighter region indicates a static surface roughness superimposed on the thermal roughness.

Journal Article↗

Thermal conductivity imaging at micrometre-scale resolution for combinatorial studies of materials.

Combinatorial methods offer an efficient approach for the development of new materials. Methods for generating combinatorial samples of materials, and methods for characterizing local composition and structure by electron microprobe analysis and electron-backscatter diffraction are relatively well developed. But a key component for combinatorial studies of materials is high-spatial-resolution measurements of the property of interest, for example, the magnetic, optical, electrical, mechanical or thermal properties of each phase, composition or processing condition. Advances in the experimental methods used for mapping these properties will have a significant impact on materials science and engineering. Here we show how time-domain thermoreflectance can be used to image the thermal conductivity of the cross-section of a Nb-Ti-Cr-Si diffusion multiple, and thereby demonstrate rapid and quantitative measurements of thermal transport properties for combinatorial studies of materials. The lateral spatial resolution of the technique is 3.4 microm, and the time required to measure a 100 x 100 pixel image is approximately 1 h. The thermal conductivity of TiCr(2) decreases by a factor of two in crossing from the near-stoichiometric side of the phase to the Ti-rich side; and the conductivity of (Ti,Nb)(3)Si shows a strong dependence on crystalline orientation.

Combinatorial Chemistry Techniques↗

Release, spread and persistence of immunoreactive neurokinin A in the dorsal horn of the cat following noxious cutaneous stimulation. Studies with antibody microprobes.

In barbiturate anaesthetized spinal cats antibody microprobes were used to examine release of immunoreactive neurokinin A following cutaneous thermal and mechanical stimulation. In the absence of peripheral stimuli, microprobes detected a diffuse basal presence of immunoreactive neurokinin A. Noxious mechanical and to a lesser extent noxious thermal stimuli increased the levels of immunoreactive neurokinin A diffusely throughout the dorsal horn which, in many cases, spread into the adjacent white matter. These diffuse stimulus-evoked increases contrast with previous experiments where the same stimuli produced discrete focal increases in levels of immunoreactive substance P. Evidence was obtained that released immunoreactive neurokinin A persisted in the spinal cord for at least 30 min beyond the period of stimulation. Neurokinin A needs consideration as the agent responsible for the long-lasting increases in excitability of some spinal neurons found by several laboratories to follow a brief input from unmyelinated primary afferents.

Animals↗