Biomedical subjects

J Thoen

Publications and source records attributed to J Thoen.

At least 19 recordsLinked to original sources

PubMed2006

Contrast-enhanced dynamic magnetic resonance imaging of finger joints in osteoarthritis and rheumatoid arthritis: an analysis based on pharmacokinetic modeling.

PURPOSE: To investigate a two-compartment kinetic model applied to the dynamic time course of contrast enhancement as a method to differentiate between finger-joint synovitis in established osteoarthritis (OA) and rheumatoid arthritis (RA). MATERIAL AND METHODS: Dynamic contrast-enhanced magnetic resonance imaging (DCE-MRI) of one hand in 19 patients and six healthy volunteers was undertaken. Eight patients had OA of the hand and eleven patients had RA. From the signal intensity curves, the three parameters Kps (endothelial transfer constant), Kep (elimination rate constant from extracellular space back to plasma) and Kel (elimination rate constant from plasma by renal excretion) were calculated. RESULTS: The rate constant Kps showed the best separation between the groups with significantly higher values in the RA group compared to the OA group (P<0.005) and in the OA group compared to the control group (P<0.005). Significantly higher values of Kep were also found in the RA group compared with the OA group (P<0.005). CONCLUSION: DCE-MRI may provide useful information that can help differentiate synovitis in OA from synovitis in RA.

Arthritis, Rheumatoid↗

PubMed2005

Dielectric spectroscopy of aerosil-dispersed liquid crystal embedded in Anopore membranes.

The complex dielectric permittivity epsilon* values are presented for aerosil-dispersed 4-pentyl-4-cyanobiphenyl (5CB) confined in Anopore membranes. The dielectric permittivities are measured in the frequency range from 10(-2) Hz to 1 GHz at temperatures ranging from 50 degrees C down to -20 degrees C. In bulk 5CB, which has only a nematic phase, there exist two main relaxation processes: one due to the rotation of molecules around their short axes for parallel orientation of the director to the probing field and another fast relaxation process due to the librational motion of molecules for perpendicular orientation. Inside Anopore membranes both these main relaxation processes can be observed, but with subtle differences. The relaxation process due to the rotation of molecules around the short axis is faster in Anopores at all temperatures in comparison with the bulk process. Hydrophilic aerosil particles, when dispersed in the liquid-crystal (LC) phase, attach to each other via hydrogen bonds and form a three-dimensional interconnecting aerosil network, thus dividing the LC phase into small domains. Dispersing 5CB with different concentrations of hydrophilic aerosils leads to a decrease in relaxation time with aerosil concentration. In these dispersed systems a slow additional relaxation process emerges. This slow process becomes stronger with higher concentrations of aerosil. From our experiments we conclude that this process is the relaxation of 5CB molecules homeotropically aligned to the surface of the aerosil particles. In the case of 5CB-aerosil dispersions enclosed in Anopore membranes this slow process still exists and increases also with aerosil concentration. The relaxation time of the rotation of the 5CB molecules around their short axis systematically increases in these 5CB-aerosil samples in Anopore membranes with aerosil concentration from the 5CB-Anopore behavior towards the behavior observed for 5CB-aerosil dispersions. We explain the evolution as resulting from opposing tendencies from size effects (in the Anopore membranes) and disorder effects (in the aerosil dispersions).

Journal Article↗

PubMed2005

Weakly first-order character of the nematic-isotropic phase transition in liquid crystals.

The classification of phase transitions in first-order and second-order (or continuous) ones is widely used. The nematic-to-isotropic (NI) transition in liquid crystals is a weakly first-order transition, with only small discontinuities in enthalpy and specific volume at the transition which are not always easy to measure. On the other hand, fluctuation effects near the transition, typical for a continuous transition, are present because of the only weakly first-order character. In a recent paper [Phys. Rev. E 69, 022701 (2004)], it was concluded from the static dielectric permittivity in the isotropic phase near the NI transition that less polar mesogens (with little or no pretransitional effects) are characteristic for a first-order NI phase transition, whereas in the case of strongly polar ones (with large pretransitional effects) the NI transition is close to second order. In this paper, we address the question whether it is, indeed, possible to use these fluctuation effects in the isotropic phase to quantify the "strength" of a weakly first-order transition, i.e., how far it is from second order. Therefore, we measured the temperature dependence of the enthalpy near the NI transition of seven liquid crystals with adiabatic scanning calorimetry and compared the measured values of the latent heat with pretransitional effects in the dielectric constant and the specific heat capacity. The compounds used in the comparison are MBBA, 5CB, 8CB, 5NCS, 5CN, 8CHBT, and D7AB. From our analysis we find, contrary to the assertion in the above reference, no correlation between the strength of the NI transition of a given compound and the pretransitional effects observed, neither dielectrically, nor thermally.

Comment↗

PubMed2005

Effect of aerosil dispersions on the nematic-to-isotropic interface.

The effect of silica aerosils on the kinetics of the first-order nematic-isotropic (NI) phase transition is phenomenologically described in the framework of the time-dependent Landau-Ginzburg equation. A steady-state solution to the equation is presented such that the NI interface may propagate with a solitary-like wave profile under constant quenching. The results provide a plausible basis for the interpretation of the dynamical effects of quenched disorder in the liquid-crystal systems, caused by randomly interconnected porous media, such as aerosils. In the low silica aerosil rho(s) ( < or =0.1 g/cm;3) regime, the calculated values of the interface velocity v(T,rho(s)), the interface thickness kappa(T,rho(s)), and the critical radius of a spherical nucleus of new nematic phase in a bulk isotropic environment, composed of polar molecules, such as 4-n-octyl- 4(')- cyanobiphenyl and 4-n-heptyl- 4(')- cyanobiphenyl shows that the effect of silica aerosils on the kinetics is reflected in a shifting of the set of temperature-dependent curves to lower temperature values.-1.

Journal Article↗

PubMed2005

Influence of nanosized confinements on 4-n-decyl-4'-cyanobiphenyl (10CB): a broadband dielectric study.

Real (epsilon') and imaginary (epsilon") parts of the complex dielectric permittivity (epsilon*) of the liquid crystal (LC) 4-n-decyl-4'-cyanobiphenyl (10CB) embedded in Anopore membranes and Vycor porous glass, as well as dispersed with hydrophilic aerosils, have been studied by means of broadband dielectric spectroscopy in the frequency range from 10(-2) Hz to 1 GHz . In bulk 10CB, which has a direct transition from an isotropic to a smectic- A phase, there exists one main relaxation process for the parallel orientation of the director with respect to the probing field and a faster one for the perpendicular orientation. All molecular relaxation processes in 10CB are of Debye type and have Arrhenius like temperature dependence. For 10CB embedded in untreated and surface treated cylindrical pores of Anopore membranes the dielectric spectra are similar to the bulk with the exception that both the rotation around the short axis and the libration motion are faster in the pores. In the case of 10CB dispersed with two different concentrations of hydrophilic aerosils an emergence of a slow relaxation process, which is stronger for the higher concentration, is additionally observed along with the bulklike processes. The slow process in the LC-hydrophilic aerosil system is attributed to the relaxation of the molecules that are homeotropically aligned close to the surfaces of the aerosil particles. This process also has an Arrhenius type of temperature dependence. For 10CB embedded in narrow channels of Vycor porous glass three relaxation processes are observed. Two of these processes are bulklike and are due to the librational motion of molecules and the rotation of molecules around their short axes. The slowest process seems to be a surface process, similar in origin to that observed for 10CB dispersed with hydrophilic aerosils, and is prominent amongst all. The material in the Vycor porous glass could be supercooled by at least 185 degrees below bulk crystallization temperature. The slow process has a Vogel-Fulcher-Tamman (VFT) type of temperature dependence typical for glass formers in this wide temperature range. In addition, the bulklike processes are found to be strongly modified and also have a VFT like temperature dependence from measurements done in a wide temperature range. This behavior is in contrast to other reports of glassy behavior in confined LC, where the glassy behavior as concluded from a slow relaxation process observed in a narrow temperature range.

Journal Article↗

PubMed2005

Static and dynamic thermal quantities near the consolute point of the binary liquid mixture aniline-cyclohexane studied with a photopyroelectric technique and adiabatic scanning calorimetry.

We studied the thermal conductivity, thermal effusivity, and specific heat capacity at constant pressure of the critical binary liquid mixture aniline-cyclohexane near the consolute point, using a photopyroelectric (PPE) technique and adiabatic scanning calorimetry (ASC). According to recent theoretical predictions based on renormalization group theory calculations, a substantial (but not diverging) enhancement in the thermal conductivity in the homogeneous phase near the critical temperature was expected for this binary system near the consolute point. However, within an experimental precision of 0.05%, we found no deviation from linear behavior in the range of 5 K above Tc down to Tc. The specific heat capacity calculated from the results for the thermal conductivity and effusivity is in good agreement with that measured by ASC. For the ASC results, the theoretical power law expression with the Ising critical exponent was fitted to the specific heat capacity both above and below the transition temperature. Good agreement with theory was found both for the amplitude ratio and the two-scale universality.

Journal Article↗

PubMed2005

Characterization of the smectic-A-hexatic-B transition in 650BC by adiabatic scanning calorimetry.

We investigated the smectic-A-hexatic-B (SmA-HexB) transition in the liquid-crystal n-hexyl-4'-n-pentyloxybiphenyl-4-carboxilate (650BC) with adiabatic scanning calorimetry. We were able to prove in a direct way that this transition is indeed very weakly first order, as was already suggested in the literature. The latent heat at the transition was determined to be deltaHL = 0.04 +/- 0.02 J/g. Our experiments confirm the high value for the heat capacity critical exponent earlier reported, yielding alpha = 0.64 +/- 0.05.

Journal Article↗

PubMed2004

Thermal conductivity, thermal effusivity, and specific heat capacity near the lower critical point of the binary liquid mixture n-butoxyethanol-water.

Experimental investigations on binary liquid mixtures near the critical mixing point are presently leading to a controversy about the anomaly in the thermal conductivity. A photopyroelectric technique is used to determine the thermal conductivity and the effusivity of the binary liquid mixture n-butoxyethanol-water at its critical concentration near the critical mixing point. It is proven that, contrary to previous reports, there is no critical enhancement in the thermal conductivity. The specific heat capacity is calculated from these results and compared with the results from measurements performed by adiabatic scanning calorimetry.

Journal Article↗

PubMed2004

Pretransitional anomalies in the shear flow near a second-order nematic-smectic- a phase change.

Pretransitional anomalies in a shear flow near a second order nematic-smectic- A ( NA ) phase transition temperature T(NA), for liquid crystals (LC's), taking into account the fluctuations of the local smectic order parameter above the T(NA), are investigated. It is shown that the tumbling instability of the Couette shear flow for polar LC compounds, such as 4-n-octyl- 4(') -cyanobiphenyl (8CB), in the vicinity of T(NA), e.g., at a few tens of mK from T(NA) in the nematic phase, occurs at any shear rate gamma;.

Journal Article↗

PubMed2004

Broadband dielectric spectroscopy study of molecular dynamics in the glass-forming liquid crystal isopentylcyanobiphenyl dispersed with aerosils.

The glass-forming liquid crystal isopentylcyanobiphenyl (CB15) filled with different concentrations of hydrophilic and hydrophobic aerosils has been investigated by broadband dielectric spectroscopy in the frequency range from 10(-2) Hz to 10(7) Hz over a temperature range of 173 K-300 K. CB15 that consists of chiral molecules has a monotropic system of phases nematic (N*) and smectic-A upon supercooling and forms a glass further on. In the isotropic phase a single Davidson-Cole process exists in the substance, which is due to the rotation of the molecules around their short axes. In the supercooled N* phase a Cole-Cole process that is an order of magnitude faster is additionally present and is due to the rotation in a cone around the local director. The relaxation times of the process due to rotation around short axes obey the empirical Vogel-Fulcher-Tamman behavior typical for glass-forming systems. Filling of the liquid crystal (LC) with different concentrations of hydrophilic aerosils leads to the emergence of a slow relaxation process that grows with the increasing concentration of the aerosils. The aerosil particles, which form a three-dimensional network dividing the LC phase into domains, have little effect on the relaxation times of the bulk processes. As a consequence the glass transition temperature is merely affected. On the other hand, in LCs dispersed with hydrophobic aerosils the slow process is quite weak. The slow process is attributed to the relaxation of the molecules that are homeotropically attached at the surfaces of the aerosil particles. The LC-aerosil surface interaction leads to a considerable slowing down of the molecular rotation around their short axis. The process has an Arrhenius-like temperature dependence of the relaxation times with an activated type of dynamics, which can be explained by considering a nonincreasing rearranging region of cooperativity in surface layers.

Journal Article↗

PubMed2004

Thermal relaxation of glycerol and propylene glycol studied by photothermal spectroscopy.

In this paper we report on experimental data for the frequency and temperature dependence of the thermal properties of supercooled glycerol and propylene glycol. By using a photopyroelectric method the specific heat capacity and thermal conductivity were separately determined in a bandwidth of several decades. We have recently shown that the thermal conductivity has no relaxation behavior, which simplifies the analysis of our results. The relaxation behavior of the specific heat capacity is compared with literature results for other physical quantities and a detailed analysis of the temperature dependence of the relaxation parameters is presented.

Glycerol↗

PubMed2004

Effect of silica aerosils on the nematic to isotropic transition: A theoretical treatment.

The effect of silica aerosils on a first-order nematic-isotropic (NI) transition temperature shift DeltaT(NI)(rho(s)) and on the enthalpy jump DeltaH(rho(s)) is phenomenologically described in the framework of the Landau-de Gennes theory. It is shown that the aerosil network dispersed in the liquid crystal phase creates an additional curvature perturbation, resulting in linear and nonlinear slopes both in the transition temperature shift DeltaT(NI)(rho(s))=-T(NI)(0)alpharho(s) and in the enthalpy jump DeltaH(rho(s))=1 / 4DeltaH(0)(1+sqrt[1-kapparho(s)])(2)(1-alpharho(s)), where rho(s) is the aerosil density, and both alpha and kappa are constants of the theory. In the low rho(s)(</=0.2 g/cm(3)) regime, both the calculated and the measured values of DeltaH(rho(s)) for polar liquid crystals, such as 4-n-octyl-4(')-cyanobiphenyl (8CB) and 4-n-heptyl-4(')-cyanobiphenyl (7CB) show a good agreement between theory and experiment. The comparisons between the calculated and measured values of DeltaT(NI)(rho(s)), in the low-rho(s) regime, show a better agreement in the 7CB+aerosil than in the 8CB+aerosil systems.

Journal Article↗

PubMed2003

First-order character of the smectic-A to chiral nematic transition in chiral liquid-crystal mixtures.

An investigation into the smectic-A to chiral nematic (N'A) transition in liquid crystals is presented by using adiabatic scanning calorimetry (ASC). It is predicted theoretically that chirality drives this transition to first order. This transition is studied in mixtures of the nonchiral liquid crystal octyloxycyanobiphenyl (8OCB) and the chiral 4-(2-methylbutyl)-4(')-cyanobiphenyl (CB15), a system with a large (chiral) nematic region that widens upon increasing the chiral (CB15) fraction. An ASC measurement on pure 8OCB showed no evidence for a latent heat, in agreement with previous ac calorimetric studies, with an upper boundary for the latent heat (if any) of 1.8 J/kg. Since pure 8OCB has no measurable latent heat, and taking into account the widening of the chiral nematic region, the possibility of a continuous to first-order crossover due to the coupling of the nematic and the smectic order parameters, as occurring in several cases of smectic-A to nematic (NA) transitions, can be excluded. However, for all examined mixtures a latent heat could be determined at the smectic-A to chiral nematic transition. This confirms theoretical predictions of the first order character of this transition. Quantitatively, theoretical predictions of the evolution of the entropy discontinuities and latent heats of this transition were not consistent with the experimental results. It was further observed that the transition temperature decreases linearly in agreement with theoretical predictions and a previous ac calorimetric study. Finally, it was observed that the pretransitional specific heat capacity shows an interesting evolution upon increasing chiral fraction, and it may be concluded that any theoretical model based on Landau theory is not sufficient to describe this transition.

Journal Article↗

PubMed2002

Systematic calorimetric investigation of the effect of silica aerosils on the nematic to isotropic transition in heptylcyanobiphenyl.

The effect of confinement on liquid crystal phase transitions was investigated in mixtures of the liquid crystal heptylcyanobiphenyl with hydrophilic aerosils. The influence of the aerosil density on the nematic to isotropic transition was studied by adiabatic scanning calorimetry. Mixtures have been investigated with an aerosil content between rho(S)=0.1 and rho(S)=0.7, the latter being substantially higher than that investigated in previous studies with other liquid crystal-aerosil mixtures. The transitions in the examined mixtures exhibited an unusually large broadening, while the transition temperatures showed peculiar behavior. Notwithstanding, the transition (latent) heat behaved as could be expected on the basis of previous studies. The observed behavior can be explained, in the context of the elastic-strain approach usually employed to describe transition temperature shifts, by variations in the distribution of the radius of curvature R of the aerosil voids originating from sample preparation. It is important in this regard to separate the behavior of the transition temperatures and the transition (latent) heats, the former being influenced by the radius of curvature of the voids and the latter by the total void surface per unit volume. Three quantitative models were compared with experimental results. Both the pinned boundary layer and the random field model yield an evolution of transition temperatures not in agreement with experimental observations. More importantly, they predict a decrease of the pretransitional specific heat capacity, not supported by experiment. The difficulties with these models are avoided in a third, mean-field surface-induced order model.

Journal Article↗

PubMed2002

Photopyroelectric ac calorimetric study of the nematic-smectic-A phase-transition line in binary liquid crystal mixtures with injected smectic-A phases.

Using a recently developed photopyroelectric ac calorimetric technique we investigate two binary liquid crystal mixtures with so-called injected smectic-A phases. Characteristic of these systems is the occurrence of nematic-to-smectic-A transition lines in the phase diagram of mixtures of pure compounds having only a nematic phase. The two binary systems are pentylcyanobiphenyl with either 4-n-propylcyclohexyl-carboxylate or 4-n-pentylphenyl 4(')-n-pentyloxybenzoate. Both these systems have domelike smectic-A ranges with narrow nematic ranges at the top. Near the top the N-SmA transitions are of first order and are crossing over to second order at a tricritical point on either side of the top with the increasing width of the nematic range. The obtained critical exponents are almost completely Fisher renormalized because of the strong concentration dependence of the nematic-to-smectic-A transition temperatures.

Journal Article↗

PubMed2002

Surface-induced smectic-ordering effect in thin nematic liquid-crystal cell.

The influence of the surface-induced smectic A (SmA) phase on the threshold field, for homeotropic alignment of polar liquid crystals is discussed from the energy point of view. It is shown that the Freedericksz critical field, for 4-n-octyl-4'-cyanobiphenyl (8CB), in a very thin cell near the second-order nematic-SmA phase transition, exhibits an anomalous increase with decreasing of temperature.

Journal Article↗

PubMed2001

Effect of silica aerosil dispersions on the dielectric properties of a nematic liquid crystal.

The static and dynamic aspects of (4-n-heptyl-4'-cyanobiphenyl) (7CB) perturbed by the dispersion of 70-A-diameter hydrophilic silica aerosil spheres have been investigated using dielectric spectroscopy. Results on five mixtures of 7CB plus silica aerosil are presented in order to probe systematically the disorder introduced by the silica aerosil network on the 7CB molecules. Measurements on homeotropically aligned samples have been made from 75 kHz to 30 MHz in the temperature range 30-60 degrees C. It was found for the mixtures that the nematic-isotropic transition temperature is lower than that of the bulk 7CB. Bulklike relaxation processes due to the rotation of the molecules around the short axis have been analyzed, and were found to follow Arrhenius-type behavior in the nematic phase except in the vicinity of the nematic-isotropic transition temperature. These processes are slightly faster in the mixture than in the free phase. A dielectric process in the low frequency range, absent in the bulk, has been observed in samples with higher silica concentration. All the observed relaxation processes in the mixtures are of non-Debye type.

Journal Article↗

PubMed2001

A preliminary study of circadian serum cortisol concentrations in response to a 72-hour fast in rheumatoid arthritis patients not previously treated with corticosteroids.

The aim of the study was to investigate the effects a 72-h fast upon serum total and free cortisol concentrations in RA patients not previously treated with glucocorticoids. Total serum cortisol and transcortin concentrations were measured in four RA patients with active disease at 4-h intervals during two 24-h periods (1200 h-1200 h), the first while eating a normal diet (fed state) and the second during the last 24 h of a 72-h water fast. Free cortisol concentrations were calculated from the total cortisol and transcortin values. The 3-day fast increased overall 24-h free and total cortisol concentrations by 50% and 35%, respectively. This was due largely to a marked increase in nocturnal serum cortisol concentrations during fasting, particularly at 0400 h, when mean total and free cortisol levels were increased by 170% and 260% compared to the fed state. Between 2000 and 0800 h overall total- and free cortisol concentrations were increased by 72% and 99%, respectively. These results suggest that an increase in nocturnal concentrations of cortisol occurs in response to fasting in RA patients not previously treated with glucocorticoids. These increases may mediate the beneficial clinical response previously found in studies of longer fasting periods in RA patients.

Adult↗