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Influence of 4-methacryloxyethyl trimellitic anhydride on composites subjected to hygrothermal cycling.

Pastes were made by spatulating a hydroxyapatite powder into triethylene glycol dimethacrylate (TEGDMA) that contained benzoyl peroxide. For comparison, similar pastes included 5 wt-% 4-methacryloxyethyl trimellitic anhydride (4-META) in the TEGDMA. Composites were made by heating at 120 degrees C under pressure. Inclusion of 4-META reduced the rate of diffusion of water by about one-third, at 27 degrees C. Also after thermal cycling in water, inclusion of 4-META decreased the fractional drop in compressive strength by about one-half. Examination of fracture surfaces indicated that inclusion of 4-META improved the wetting of filler particles and gave more coherent composites. All these findings are consistent with the view that 4-META acts as a coupling agent.

Acrylates↗

Microrheology of polyethylene oxide using diffusing wave spectroscopy and single scattering.

Experiments investigating the local viscoelastic properties of a simple uncross-linked flexible polymer are performed on polyethylene oxide solutions in the semidilute regime using polystyrene beads of varying sizes and surface chemistry as probes. We measure the thermal motions of the beads to obtain the elastic and viscous moduli of our sample. Two different dynamic light scattering techniques, diffusing wave spectroscopy and quasielastic light scattering (QELS), are used to determine the dynamics of the probe particles. Diffusing wave spectroscopy probes the short time dynamics of the scatterers while QELS or single scattering measures the dynamics at larger times. This results in a larger frequency overlap of the data obtained from the microrheological techniques with the data obtained from the conventional bulk measurements. The moduli are estimated using a modified algebraic form of the generalized Stokes-Einstein equation. Comparison of microrheology with bulk measurements shows excellent similarity confirming the applicability of this method for simple, uncross-linked polymeric systems.

Journal Article↗

Extended theory of selective photothermolysis.

BACKGROUND AND OBJECTIVE: We present a new theory of selective thermal damage of non-uniformly pigmented structures in biological tissues. Spatial separation of the heavily pigmented areas and the target requires limitation of the pigment temperature and heat diffusion from the pigmented to the targeted areas. STUDY DESIGNS/MATERIALS AND METHODS: A concept of selective target damage by heat diffusion is presented for three target geometries: planar, cylindrical, and spherical. An in vitro experiment is described in which the dependence of thermal damage on pulsewidth at constant fluence was evaluated. RESULTS: The in vitro experiment showed that the size of the damage zone for similar hair follicles was pulsewidth-independent over a very broad range of pulsewidths (30-400 ms). We formulated a new theory (extended theory of photothermolysis) to interpret the experimental results. CONCLUSIONS: Based on this new theory, the treatment pulsewidth for non-uniformly pigmented targets is significantly longer than the target thermal relaxation time (TRT). The theory provides new recommendations for photoepilation and photosclerotherapy parameters.

Cadaver↗

Photoinduced electron transfer competitive with energy transfer of the excited triplet state of [60]fullerene to ferrocene derivatives revealed by combination of transient absorption and thermal lens measurements.

The quenching processes of the exited triplet state of fullerene (3C60) by ferrocene (Fc) derivatives have been observed by the transient absorption spectroscopy and thermal lens methods. Although 3C60 was efficiently quenched by Fc in the rate close to the diffusion controlled limit, the quantum yields (phi(et)) for the generation of the radical anion of C60 (C60*-) via 3C60 were quite low even in polar solvents; nevertheless, the free-energy changes (deltaG(et)) of electron transfer from Fc to 3C60 are sufficiently negative. In benzonitrile (BN), the phi(et) value for unsubstitued Fc was less than 0.1. The thermal lens method indicates that energy transfer from 3C60 to Fc takes place efficiently, suggesting that the excited triplet energy level of Fc was lower than that of 3C60. Therefore, energy transfer from 3C60 to ferrocene decreases the electron-transfer process from ferrocene to 3C60. To increase the participation of electron transfer, introduction of electron-donor substituents to Fc (phi(et) = 0.46 for decamethylferrocene in BN) and an increase in solvent polarity (phi(et) = 0.58 in BN:DMF (1:2) for decamethylferrocene) were effective.

Journal Article↗

Diffusiophoresis of two-dimensional liquid droplets in a phase-separating system.

The motion of phase-separating liquid drops was simulated in two dimensions following the model H, where convection and diffusion are coupled via a body force, expressing the tendency of demixing systems to minimize their free energy. This driving force depends on the capillary number, i.e., the ratio of viscous to thermal forces, which in a typical case is of order 10(-4), inducing a convective material flux much larger than its diffusive counterpart. Three problems were considered. In the first, we studied the motion of a single drop immersed in a continuum field with constant concentration gradient, finding that the drop speed is proportional to the concentration gradient and inversely proportional to the capillary number. In the second problem, we found that the motion of a single drop immersed in a homogeneous concentration field depends on the difference (Delta(phi))(0) between the initial concentration of the continuum phase and its equilibrium value. In fact, when (Delta(phi))(0)<0, the drop shrinks without moving, while when (Delta(phi))(0)>0, the drop consumes material from the surrounding field and moves randomly, propelled by the induced capillary driving force. During its movement, the drop grows linearly in time, with a growth rate proportional to the ratio between molecular diffusivity and interface thickness. In addition, during its random motion, the drop mean square displacement grows linearly with time, with an effective diffusion coefficient which is of the same magnitude as the molecular diffusivity. The predicted drop growth rate and mean velocity are in good agreement with experimental observations. Finally, the motion of two drops is studied, showing that the capillary forces induce a mutual attraction between the two drops. When (Delta(phi))(0)<0, the attractive force is unchallenged, thus leading always to coalescence, while when (Delta(phi))(0)>0 a screening effect arises which may keep the two drops apart from each other.

Journal Article↗

[Calculation of the concentration Rayleigh number for isothermal transport processes across a polymeric membrane by a method for measuring diffusion flux in three component non-electrolytic solutions].

A method of determination critical value of concentration Rayleigh Number ((Rci)lim.) in isothermal membrane transport processes of three component non-electrolyte solutions was worked out. The method based on the derived in the paper equation, which include membrane transport coefficients (hydraulic permeability, reflection and diffusive permeability coefficients), solution parameters (viscosity coefficient, density and diffusion coefficient in solution). In order to experimental verification of these method the transport coefficients of symmetric flat polymeric membrane, parameters of solutions and diffusive flux for glucose solution in 0.2 mole/l aqueous ethanol solution were determined. Experiments were carried out by osmotic-diffusive single-membrane double-cell system. One cell in all experiments was filled with pure water while the other with the examined solutions. The experimental critical value of concentration Rayleigh Number (RCi)lim. = 1799 is comparable with theoretical critical value of thermal Rayleigh Number (TT)lim. = 1707.

Diffusion↗

Experimental evaluation of the separation efficiency in capillary electrophoresis using open tubular and gel-filled columns.

The band dispersion phenomena in capillary zone electrophoresis (CZE) using untreated and surface-treated open tubular and gel-filled capillaries were experimentally evaluated, with emphasis on small capillary diameters (10-100 microns). Laser-induced fluorescence detection was used for high-sensitivity detection of the isoindoles originated from model amino acids. The plots of plate height vs electric field strength were generated for different column radii and compared with a theoretical model for CZE. In addition to the diffusion-controlled band dispersion in the relatively low electric field range, adsorptive interactions between a solute and the capillary wall may play a certain role in band-broadening. The sorption-desorption kinetics become important with increasing electric field strength. Thermal effects appear to contribute little to band-broadening in relatively small capillaries (less than 50-microns i.d.) within normal operating voltages (less than 30 kV), but could become significant in capillaries with larger bores (greater than 75-microns i.d.). With gel-filled capillaries of small diameters (less than 50-microns i.d.), diffusion processes can be minimized. In addition, thermal effects do not appear critical in such columns at reasonable voltages.

Animals↗

Analysis of rotation-driven electrokinetic flow in microscale gap regions of rotating disk systems.

In the present study, a novel theoretical model is developed for the analysis of rotating thermal-fluid flow characteristics in the presence of electrokinetic effects in the microscale gap region between two parallel disks under specified electrostatic, rotational, and thermal boundary conditions. The major flow configuration considered is a rotor-stator disk system. Axisymmetric Navier-Stokes equations with consideration of electric body force stemming from streaming potential are employed in the momentum balance. Variations of the fluid viscosity and permittivity with the local fluid temperature are considered. Between two disks, the axial distribution of the electric potential is determined by the Poisson equation with the concentration distributions of positive and negative ions obtained from Nernst-Planck equations for convection-diffusion of the ions in the flow field. Effects of disk rotation and electrostatic and thermal conditions on the electrokinetic flow and thermal characteristics are investigated. The electrohydrodynamic mechanisms are addressed with an interpretation of the coupling nature of the electric and flow fields. Finally, solutions with electric potential determined by employing nonlinear or linearized Poisson-Boltzmann equation and/or invoking assumptions of constant properties are compared with the predictions of the present model for justification of various levels of approximation in solution of the electrothermal flow behaviors in rotating microfluidic systems.

Journal Article↗

The variance and the quantity 2Dt in capillary zone electrophoresis.

The variance is generally used as a measure of dispersion of zones in capillary zone electrophoresis (CZE). It is a quantitative measure of the separation power of a system and different causes of dispersion can be rated by their partial variances, which can be summed up to total variance. However, the additivity is only valid for independent dispersion sources, a fact that often seems to be ignored. The ubiquitous dispersion source diffusion is taken into consideration by the Einstein term 2Dt. Other sources of dispersion are, e.g., injection, detection, thermal gradients, adsorption, and hydrodynamic flow. For each of these sources various variance expressions have been derived. The origin of the term 2Dt and its relation to the variance is explained and the calculation of variance in general is discussed. The equivalence of the diffusion variance and the term 2Dt is verified with some simple initial forms of sample zone and the additivity of variances in ideal zone electrophoresis is demonstrated. The change of conductivity in zones results in asymmetrical zone forms which is an indication of nonideality of a system. It is shown that in such cases the term 2Dt is no longer valid and its use as an additive variance component leads to an erroneous total variance. Because in zone electrophoresis conductivity in a zone always changes more or less, the additivity of variances is never perfectly valid. However, in many cases the nonideality may be so small that the additivity in practice is still applicable.(ABSTRACT TRUNCATED AT 250 WORDS)

Capillary Action↗

Thermal therapy of canine cerebral tumors using a 980 nm diode laser with MR temperature-sensitive imaging feedback.

BACKGROUND AND PURPOSE: The laser-induced thermal therapy (LITT) of cerebral tumors has conventionally been performed using Nd:YAG lasers and is associated with a risk of high focal temperatures potentially followed by cavitation that could result in boiling and/or explosive char. We have developed small diffusing laser fiber tips to better distribute the energy deposition and a computer controlled feedback system to monitor therapy and prevent excess temperature buildup. In this study, we evaluated the feasibility of using magnetic resonance temperature imaging (MRTI)-based feedback system for the thermal treatment of experimental intracerebral tumors using 980 nm laser irradiation delivered through these diffusing tips. STUDY DESIGN/MATERIALS AND METHODS: Transmissible venereal tumors (TVTs) were grown via inoculation in the right cerebral hemisphere of seven canines. The laser fiber tips were inserted into a total of 10 independent TVT-suspected regions in the seven animals. Margins for the target area in each animal were prescribed on the basis of pretreatment MR images. MRTI-based feedback software was used to measure and regulate both temperature and the delivered thermal dose to achieve the desired thermal ablation and prevent excess heating. The effects of treatment were verified by results of histologic analyses. RESULTS: Treatments resulted in contiguous areas of thermal necrosis in tumors and adjacent brain margin. The feedback software successfully cut off the laser power once the desired treatment volume was achieved, and prevented focal temperatures from exceeding predefined thresholds. Follow-up MRI studies showed 1.4- to 2.9-fold LITT-induced lesion expansion within 1-6 days after treatment. CONCLUSIONS: Targeted thermal coagulation of small intracerebral tumors is feasible using MRTI-based feedback and diffused 980 nm diode laser light.

Animals↗

Capillarisation, oxygen diffusion distances and mitochondrial content of carp muscles following acclimation to summer and winter temperatures.

Many species of fish show a partial or complete thermal compensation of metabolic rate on acclimation from summer to winter temperatures. In the present study Crucian carp (Carassius carassius L.) were acclimated for two months to either 2 degrees C or 28 degrees C and the effects of temperature acclimation on mitochondrial content and capillary supply to myotomal muscles determined. Mitochondria occupy 31.4% and 14.7% of slow fibre volume in 2 degrees C- and 28 degrees C-acclimated fish, respectively. Fast muscles of cold- but not warm-acclimated fish show a marked heterogeneity in mitochondrial volume. For example, only 5% of fast fibres in 28 degrees C-acclimated fish contain 5% mitochondria compared to 34% in 2 degrees C-acclimated fish. The mean mitochondrial volume in fast fibres is 6.1% and 1.6% for cold- and warm-acclimated fish, respectively. Increases in the mitochondrial compartment with cold acclimation were accompanied by an increase in the capillary supply to both fast (1.4 to 2.9 capillaries/fibre) and slow (2.2 to 4.8 capillaries/fibre) muscles. The percentage of slow fibre surface vascularised is 13.6 in 28 degrees C-acclimated fish and 32.1 in 2 degrees C-acclimated fish. Corresponding values for fast muscle are 2.3 and 6.6% for warm- and cold-acclimated fish, respectively. Maximum hypothetical diffusion distances are reduced by approximately 23-30% in the muscles of 2 degrees C-compared to 28 degrees C-acclimated fish. However, the capillary surface supplying 1 micron 3 of mitochondria is similar at both temperatures. Factors regulating thermal compensation of aerobic metabolism and the plasticity of fish muscle to environmental change are briefly discussed.

Adaptation, Physiological↗

General aspects of the cellular response to low- and high-LET radiation.

Radiobiological studies have shown for some time that the effects of ionising radiation on cells are mainly explained by modification of the DNA. Numerous studies over the past 50 years have accumulated clear evidence of the cause-effect relationship between damage to DNA and the cytotoxic and mutagenic effects of ionising radiation. However, the path from irradiation of the cells to the induction of biological effects comprises several complex steps. The first step involves interactions between the radiation and the cellular environment. These consist of physical and chemical reactions which produce ions, excited molecules and radical species. Excitations and ionisations are complete in about 10(-15) s, and are followed by a chemical thermal equilibrium of the species produced within 10(-12) s. These species then diffuse from their site of production and provoke alterations to a variety of cellular components. This damage is detected by cellular surveillance systems, which in turn activate signalling cascades, gene transcription and enzyme recruitment, which participate in the cellular response. In most cases, cell cycle arrest occurs, allowing, according to the biological relevance of the DNA damage, either a process of DNA repair or programmed cell death (apoptosis). The accuracy of the DNA repair which is performed depends on the complexity of the DNA lesion and on the DNA repair machinery fidelity itself. Improper DNA repair can lead to mutation, chromosome aberration, genetic instability, oncogenic transformation and, ultimately, cell death.

Animals↗

Temperature acclimation and oxygen binding properties of blood of the European eel, Anguilla anguilla.

Temperature acclimation of the European eel, Anguilla anguilla, resulted in red cell GTP/Hb molar ratios of 1.20, 1.77 and 0.80 at 2, 17 and 29 degrees C, respectively. A small increase in blood oxygen capacity was present in 29 degrees C acclimated eels. The CO2 Bohr effect and the shape of the oxygen binding curve (n-Hill) were invariant with both temperature and GTP/Hb. The significant differences in the GTP/Hb ratio corresponded with a strong enhancement of the temperature effect on blood oxygen affinity between 2 and 17 degrees C and a similarly strong compensation between 17 and 29 degrees C. Predicted in vivo P50 values were 3.0, 13.8 and 17.6 mmHg at 2 degrees C, 17 and 29 degrees C, respectively. The adaptational value of these findings are discussed in relation to standard metabolic rates at the various temperatures. A tentative hypothesis is proposed that the present study confirms and expands earlier work and supports the contention that adjustments in blood oxygen affinity of thermally acclimated teleosts serve to provide them with an unloading O2 tension for diffusion closely matching the standard oxygen requirements at the various temperatures.

Acclimatization↗

Electrochemical characterization of recessed nanodisk-array electrodes prepared from track-etched membranes.

Recessed nanodisk-array electrodes (RNEs) fabricated from track-etched polycarbonate membranes (TEPCMs) having cylindrical nanopores (50 nm in diameter) were characterized using cyclic voltammetry (CV). Such electrodes were prepared by depositing a gold thin film onto a TEPCM via sputtering or thermal evaporation. CV of the RNEs showed the transition from linear to radial diffusion modes of redox-active molecules with decreasing scan rate. The resulting change in maximum faradic current, which is the peak current in a peak-shaped CV and the plateau current in a sigmoidal CV, provides a simple means for calculating the pore length and effective pore density within a RNE. This method permits us to assess the completeness of the seal between a TEPCM and gold film as well as the extent to which air bubbles block the nanopores.

Journal Article↗

Adsorption and thermal condensation mechanisms of amino acids on oxide supports. 1. Glycine on silica.

Glycine was adsorbed on the surface of a well-defined silica from aqueous solutions of variable concentrations and pHs. The adsorbed molecules were characterized using middle-IR and UV-vis-NIR spectroscopies. Except at the lowest pH (2.0), they were predominantly present on the surface as zwitterions. Two successive deposition mechanisms were evidenced with increasing glycine concentration. At low concentrations, glycine is specifically adsorbed on silica surface sites, probably through its NH3+ moiety. The pH dependence suggests that these sites may be silanolate groups (approximately equal to Si-O-). At higher concentrations, specific adsorption sites are saturated and surface-induced precipitation of beta-glycine is observed. The thermal reactivity of adsorbed/deposited glycine was then investigated by thermogravimetric analysis, in situ diffuse reflectance IR spectroscopy, and thermoprogrammed desorption coupled with mass spectrometry. Adsorbed glycine molecules react to form peptide bonds at a temperature considerably lower than that for bulk crystalline alpha-glycine. The main reaction product is the cyclic dimer diketopiperazine, with no evidence of the linear dimer. The activation mechanism is not diffusionally limited; the formation of "surface acyls", previously proposed for related systems, has not been evidenced here. These findings are of relevance for the evaluation of prebiotic peptide synthesis scenarios.

Adsorption↗

Excess-entropy-based anomalies for a waterlike fluid.

Many thermodynamic and dynamic properties of water display unusual behavior at low enough temperatures. In a recent study, Yan et al. [Phys. Rev. Lett. 95, 130604 (2005)] identified a spherically symmetric two-scale potential that displays many of the same anomalous properties as water. More specifically, for select parametrizations of the potential, one finds that the regions where isothermal compression anomalously (i) decreases the fluid's structural order, (ii) increases its translational self-diffusivity, and (iii) increases its entropy form nested domes in the temperature-density plane. These property relationships are similar to those found for more realistic models of water. In this work, the authors provide evidence that suggests that the anomalous regions specified above can all be linked through knowledge of the excess entropy. Specifically, the authors show how entropy scaling relationships developed by Rosenfeld [Phys. Rev. A 15, 2545 (1977)] can be used to describe the region of diffusivity anomalies and to predict the state conditions for which anomalous viscosity and thermal conductivity behavior might be found.

Journal Article↗

Kinetics of the crystalline-liquid crystalline phase transition of dimyristoyl L-alpha-lecithin bilayers.

Aqueous dispersions of synthetic dimyristoyl L-alpha-lecithin undergo a sharp decrease in turbidity in the temperature range where the crystalline-liquid crystalline phase transition occurs. Equilibrium transition curves, monitored by the absorbancy change at 300 nm, reproduce all the important features of a calorimetric melting curve [Hinz & Sturtevant (1972) J. Biol. Chem. 247, 6071]. A rapid temperature-jump of the dispersion, measured by the same absorbancy change, has detected several different molecular processes depending on the magnitude of the perturbation. These processes include a phase transition, permeation of ions and water across the membrane, and repture, annealing, or fusion of the bilayer structures. When the temperature-jump is limited to 1 degree, only reactions associated with the phase transition are detectable and no signal is generated after a temperature-jump except for those which end within or extend beyond the transition zones. At least two relaxation times are resolved for the phase transition reactions. The faster one in the millisecond time range is strongly temperature-dependent and has an activation energy close to one million calories per mole. The second one, in the 100-msec time range, appears to have a much smaller activation energy. These observations indicate that strongly cooperative nucleation processes and energy-dependent fast propagation steps occur during the phase transition. Since the kinetics of the transition are complex, intermediate state or transient structures must exist in the transition regions of the bilayer dispersions. These thermal fluctuations of the bilayer structures may have important effects on the lateral diffusion and permeation of molecules and ions in the membrane structure.

Chemical Phenomena↗

Velocity-fluctuation-induced anomalous kinetics of the A+A--> reaction

The effect of a random velocity field on the kinetics of the single-species annihilation reaction A+A--> is analyzed near two dimensions with the aid of the perturbative renormalization group. The previously found asymptotic behavior induced by density fluctuations only in the diffusion-limited reaction is shown to be unstable to any velocity fluctuations (including thermal fluctuations near equilibrium) in spatial dimensions d</=d(c)=2. Four different stable long-time asymptotic regimes induced by the combined effect of velocity and density fluctuations are identified and the corresponding decay rates calculated in the leading order.

Journal Article↗