Free ions in kerosene-based ferrofluid detected by impedance spectroscopy.

The influence of the free ions on the electric response of cells filled with kerosene-based ferrofluids in the low-frequency region is explored. The experimental investigations have been performed on cells limited by different types of electrodes, with the same kind of ferrofluid, by means of the impedance spectroscopy technique. The electrodes considered in our study are made of titanium, platinum, gold, brass and surgical steel. The analysis of the spectra of the real and imaginary parts of the electric impedance of the cell data has been done by means of a simplified version of the Poisson-Nernst-Planck model, in which only the carriers of a given sign are mobile. The agreement between the theoretical predictions and the experimental data is rather good on the whole frequency range. From the analysis of the data in the low-frequency range, dominated by the properties of the electrodes, we discovered that only gold electrodes behave in a manner different from the other electrodes. From the best fit of the experimental data the free-ions density is determined as well as their diffusion coefficient in kerosene. The estimated dielectric constant of the kerosene is in good agreement with the values reported in the literature. In the framework of our model, the surface conductivity of the electrodes has been also determined.

Magnetic, structural and cation distribution studies on [Formula: see text] (x = 0.00, 0.02, 0.04, 0.06 and 0.1) nanoparticles.

We synthesized and characterized the colloidal suspensions of [Formula: see text] nanoparticles with x = 0.00, 0.02, 0.04, 0.06 and 0.1. The effect of the Fe3+ ion replacement by Nd3+ on the crystal structure is in-depth studied. The samples were characterized by the following techniques: X-ray diffraction (XRD), UV-Vis spectrophotometry, transmission electronic microscopy (TEM), small-angle X-ray scattering (SAXS), magnetization as a function of applied magnetic field (M-H loops) and magnetization as a function of temperature in zero-field-cooled and field-cooled regimes (ZFC-FC). From XRD cation distribution, structural parameters were extracted. The increasing in the bandgap is interpreted as a result of the higher interatomic separation with the doping. TEM micrographs reveal a polydisperse size and shape distribution of particles. The results for the volume-weighted average diameter measured by SAXS are consistent with those determined by XRD. From the M-H loops we found that the superparamagnetic (SPM) regime contributes with 95-97% for all samples, while only 3-5% contribution comes from the paramagnetic (PM) regime. The saturation magnetization increases in a steady manner upon increasing the Nd3+ ion molar ratio from 0.00 up to 0.06, reaching the maximum value of 105.8±0.4 Am2/kg at x = 0.06. It is worth to mention that the result for the saturation magnetization value are higher than that of the bulk material.

Temperature dependence of the Soret coefficient of ionic colloids.

The temperature dependence of the Soret coefficient S(T)(T) in electrostatically charged magnetic colloids is investigated. Two different ferrofluids, with different particles' mean dimensions, are studied. In both cases we obtain a thermophilic behavior of the Soret effect. The temperature dependence of the Soret coefficient is described assuming that the nanoparticles migrate along the ionic thermoelectric field created by the thermal gradient. A model based on the contributions from the thermoelectrophoresis and variation of the double-layer energy, without fitting parameters, is used to describe the experimental results of the colloid with the bigger particles. To do so, independent measurements of the ζ potential, mass diffusion coefficient, and Seebeck coefficient are performed. The agreement of the theory and the experimental results is rather good. In the case of the ferrofluid with smaller particles, it is not possible to get experimentally reliable values of the ζ potential and the model described is used to evaluate this parameter and its temperature dependence.

Magnetic and structural study of electric double-layered ferrofluid with MnFe(2)O(4)@γ-Fe(2)O(3) nanoparticles of different mean diameters: Determination of the magnetic correlation distance.

Magnetic fluids based on manganese ferrite nanoparticles were studied from the structural point of view through small angle x-rays scattering (SAXS) and from the magnetic point of view through zero-field cooling and field cooling (ZFC-FC) and ac susceptibility measurements (MS). Three different colloids with particles mean diameters of 2.78,3.42, and 6.15 nm were investigated. The size distribution obtained from SAXS measurements follows a log-normal behavior. The ZFC-FC and MS results revealed the presence of an important magnetic interaction between the nanoparticles, characterized by a magnetic correlation distance Λ. The colloidal medium can be pictures as composed by magnetic cluster constituted by N interacting particles. These magnetic clusters are not characterized by a physical aggregation of particles. The energy barrier energy obtained is consistent with the existence of this magnetic clusters. Besides the magnetic interaction between particles, confinement effects must be included to account for the experimental values of the magnetic energy barrier encountered.

Thermodiffusion in positively charged magnetic colloids: influence of the particle diameter.

The Soret coefficient (ST) of positively charged magnetic colloids was measured as a function of the nanoparticles' diameter. The Z-scan technique and the generalization of the thermal lens model proved to be a reliable technique to measure ST. We show that ST is negative and increases with the particle's diameter, being best described by a functional dependence of the type ST∝d0. Potentiometric and conductometric experiments show that the particle's surface charge decreases as the temperature increases, changing the electrostatic interaction between the nanoparticles. The temperature gradient imposed in the ferrofluid by the Gaussian laser beam leads to the formation of the particle's concentration gradient. The origin of this phenomenon is discussed in terms of the decrease of the particle's surface charge in the hottest region of the sample and the thermoelectric field due to the inhomogeneous distribution of hydrogenous ions present in the colloidal suspension.

Dynamic light scattering and viscosity measurements in a ternary and quaternary discotic lyotropic nematic liquid crystal: tuning the backflow with salt.

Using a dynamic light scattering technique, we measure the damping rate of thermal fluctuations of the nematic director for the so-called disklike nematic N(D) phase of both the ternary lyotropic K-laurate-1-decanol-H(2)O system and the quaternary one of similar composition except for the addition of salt (K(2)SO(4)). By varying the scattering angle in suitable geometries and polarizations, we are able to measure the orientational diffusivities associated with the pure deformations of splay and twist. A previous study made in the N(D) phase of the same ternary system yielded a large deviation between the splay and twist diffusivities. The effect was then interpreted in terms of the anisotropy between their associated viscosities due to induced flows, or backflow. In the present work we observe a strong increase of the backflow as an effect of the added salt. In addition, we make auxiliary measurements of shear viscosity and magnetic instabilities, which help to characterize the effect of the salt in the orientational diffusivities as they are mixed quantities involving elastic constants and viscosity coefficients.

Differences in synthesis and absorption of cholesterol of two effective lipid-lowering therapies

Effective statin therapy is associated with a marked reduction of cardiovascular events. However, the explanation for full benefits obtained for LDL cholesterol targets by combined lipid-lowering therapy is controversial. Our study compared the effects of two equally effective lipid-lowering strategies on markers of cholesterol synthesis and absorption. A prospective, open label, randomized, parallel design study, with blinded endpoints, included 116 subjects. We compared the effects of a 12-week treatment with 40 mg rosuvastatin or the combination of 40 mg simvastatin/10 mg ezetimibe on markers of cholesterol absorption (campesterol and β-sitosterol), synthesis (desmosterol), and their ratios to cholesterol. Both therapies similarly decreased total and LDL cholesterol, triglycerides and apolipoprotein B, and increased apolipoprotein A1 (P < 0.05 vs baseline for all). Simvastatin/ezetimibe increased plasma desmosterol (P = 0.012 vs baseline), and decreased campesterol and β-sitosterol (P < 0.0001 vs baseline for both), with higher desmosterol (P = 0.007) and lower campesterol and β-sitosterol compared to rosuvastatin, (P < 0.0001, for both). In addition, rosuvastatin increased the ratios of these markers to cholesterol (P < 0.002 vs baseline for all), whereas simvastatin/ezetimibe significantly decreased the campesterol/cholesterol ratio (P = 0.008 vs baseline) and tripled the desmosterol/cholesterol ratio (P < 0.0001 vs baseline). The campesterol/cholesterol and β-sitosterol/cholesterol ratios were lower, whereas the desmosterol/cholesterol ratio was higher in patients receiving simvastatin/ezetimibe (P < 0.0001 vs rosuvastatin, for all). Pronounced differences in markers of cholesterol absorption and synthesis were observed between two equally effective lipid-lowering strategies.

Differences in synthesis and absorption of cholesterol of two effective lipid-lowering therapies.

Effective statin therapy is associated with a marked reduction of cardiovascular events. However, the explanation for full benefits obtained for LDL cholesterol targets by combined lipid-lowering therapy is controversial. Our study compared the effects of two equally effective lipid-lowering strategies on markers of cholesterol synthesis and absorption. A prospective, open label, randomized, parallel design study, with blinded endpoints, included 116 subjects. We compared the effects of a 12-week treatment with 40 mg rosuvastatin or the combination of 40 mg simvastatin/10 mg ezetimibe on markers of cholesterol absorption (campesterol and ß-sitosterol), synthesis (desmosterol), and their ratios to cholesterol. Both therapies similarly decreased total and LDL cholesterol, triglycerides and apolipoprotein B, and increased apolipoprotein A1 (P < 0.05 vs baseline for all). Simvastatin/ezetimibe increased plasma desmosterol (P = 0.012 vs baseline), and decreased campesterol and ß-sitosterol (P < 0.0001 vs baseline for both), with higher desmosterol (P = 0.007) and lower campesterol and ß-sitosterol compared to rosuvastatin, (P < 0.0001, for both). In addition, rosuvastatin increased the ratios of these markers to cholesterol (P < 0.002 vs baseline for all), whereas simvastatin/ezetimibe significantly decreased the campesterol/cholesterol ratio (P = 0.008 vs baseline) and tripled the desmosterol/cholesterol ratio (P < 0.0001 vs baseline). The campesterol/cholesterol and ß-sitosterol/cholesterol ratios were lower, whereas the desmosterol/cholesterol ratio was higher in patients receiving simvastatin/ezetimibe (P < 0.0001 vs rosuvastatin, for all). Pronounced differences in markers of cholesterol absorption and synthesis were observed between two equally effective lipid-lowering strategies.

Lyotropic mixture made of potassium laurate/1-undecanol/K2SO4/water presenting high birefringences and large biaxial nematic phase domain: a laser conoscopy study.

The lyotropic liquid crystalline quaternary mixture made of potassium laurate (KL), potassium sulphate, 1-undecanol and water was investigated by experimental optical methods (optical microscopy and laser conoscopy). In a particular temperature and relative concentrations range, the three nematic phases (two uniaxial and one biaxial) were identified. The biaxial domain in the temperature/KL concentration surface is larger when compared to other lyotropic mixtures. Moreover, this new mixture gives nematic phases with higher birefringence than similar systems. The behavior of the symmetric tensor order parameter invariants σ (3) and σ (2) calculated from the measured optical birefringences supports that the uniaxial-to-biaxial transitions are of second order, described by a mean-field theory.

Tricritical-like behavior of the nonlinear optical refraction at the nematic-isotropic transition in the E7 thermotropic liquid crystal.

We use Z-scan technique to investigate the nonlinear optical response of the thermotropic liquid crystal E7 in the neighborhood of the nematic-isotropic phase transition. The analysis of the data for the nonlinear optical birefringence is compatible with an effective critical exponent of the order parameter, ß = 0.28 ± 0.03, which is close to the classical value, ß = 0.25 , for a tricritical point. The nonlinear optical absorption in the nematic range depends on the geometrical configuration of the nematic director with respect to the polarization beam, and vanishes in the isotropic phase.

The influence of adsorption phenomena on the impedance spectroscopy of an electrolytic cell.

In this work we investigate the influence of the adsorption of ions on the impedance spectroscopy of an electrolytic cell. We consider that the positive and negative ions present in a dielectric liquid are adsorbed in the electrode surfaces with different adsorption energies. This difference in adsorption energies causes an additional plateaux in the limit of the low-frequency range of the real part of the impedance Z. In the same frequency range, a second minimum in the imaginary part of Z is predicted. The theory is illustrated with measurements of the impedance of an electrolytic solution in the frequency range from 10(-2) Hz to 1 KHz. A comparison between the present model and others from the literature to describe the experimental results is also made.

Characterization of the biocompatible magnetic colloid on the basis of Fe3O4 nanoparticles coated with dextran, used as contrast agent in magnetic resonance imaging.

The magnetic resonance imaging contrast agent, the so-called Endorem colloidal suspension on the basis of superparamagnetic iron oxide nanoparticles (mean diameter of 5.5 nm) coated with dextran, were characterized on the basis of several measurement techniques to determine the parameters of their most important physical and chemical properties. It is assumed that each nanoparticle is consisted of Fe3O4 monodomain and it was observed that its oxidation to gamma-Fe2O3 occurs at 253.1 degrees C. The Mössbauer spectroscopy have shown a superparamagnetic behavior of the magnetic nanoparticles. The Magnetic Resonance results show an increase of the relaxation times T1, T2, and T2* with decreasing concentration of iron oxide nanoparticles. The relaxation effects of SPIONs contrast agents are influenced by their local concentration as well as the applied field strength and the environment in which these agents interact with surrounding protons. The proton relaxation rates presented a linear behavior with concentration. The measured values of thermo-optic coefficient dn/dT, thermal conductivity kappa, optical birefringence delta n0, nonlinear refractive index n2, nonlinear absorption beta' and third-order nonlinear susceptibility |chi(3)| are also reported.

Thermodiffusion in a multicomponent lyotropic mixture in the vicinity of the critical micellar concentration by using the Z -scan technique.

Thermodiffusion in a lyotropic mixture of water and potassium laurate is investigated by means of an optical technique (Z scan) distinguishing the index variations due to the temperature gradient and the mass gradients. A phenomenological framework allowing for coupled diffusion is developed in order to analyze thermodiffusion in multicomponent systems. An observable parameter relating to the mass gradients is found to exhibit a sharp change around the critical micellar concentration, and thus may be used to detect it. The change in the slope is due to the markedly different values of the Soret coefficients of the surfactant and the micelles. The difference in the Soret coefficients is due to the fact that the micellization process reduces the energy of interaction of the ball of amphiphilic molecules with the solvent.

Novel fluorescent probe for low density lipoprotein, based on the enhancement of Europium emission band.

We report here the observation of the enhancement of Europium-tetracycline complex emission in Low Density Lipoprotein (LDL) solutions. Europium emission band of tetracycline solution containing Europium (III) chloride hexahydrate was tested to obtain effective enhancement in the presence of native LDL and oxidized LDL. Europium emission lifetime in the presence of lipoproteins was measured, resulting in a simple method to measure the lipoproteins quantity in an aqueous solution at physiological pH. This method shows that the complex can be used as a sensor to determine the different states of native and oxidized LDL in biological fluids.

Relaxation time for the ionic current in a nematic cell under a large electric field.

We evaluate the ionic relaxation time of a nematic cell subjected to a potential difference, V0 , very large with respect to VT=KBT/q=0.025 V, where KBT is the thermal energy, and q the electrical charge of the ions, assumed monovalent. The analysis is performed by assuming that the mobilities of the positive and negative ions are the same, and that the ions can be considered pointlike. We show that, for V0>>VT, the relaxation time tends to the time of flight of the ions. In our analysis the ionic charges are assumed to form two surface layers responsible for a partial screening of the external field. In this framework, the evolution of the surface-charge density is determined by a simple differential equation related to the conservation of the ions number. According to our calculations, the relaxation time of the surface density of ionic origin, and of the electrical potential close to the electrodes, depends on the applied voltage, in agreement with the experimental observations.

Micellar anisometry in lyotropic uniaxial nematic phases studied by transversal NMR relaxation dispersion.

A new method, based on the measurement of the (23 )( )Na nuclei spin-spin NMR relaxation times ( T2 ), is proposed to investigate the shape of micelles in lyotropic nematic phases. We investigate the ternary lyotropic mixture of sodium dodecyl sulfate, 1-decanol, and water by using the NMR technique, measuring T2 in the two lyotropic uniaxial nematic phases. The characteristic relaxation time curves of each particular phase are analyzed by considering that they are constituted by a superposition of exponential decays with typical characteristic times: in a sense, a T2 spectroscopy. The analysis of the T2 dispersion profiles in both the uniaxial nematic calamitic and discotic phases indicates that our results can be interpreted in terms of the model of intrinsically biaxial micelles in all the nematic phases.

Effect of the concentration of magnetic grains on the linear-optical-absorption coefficient of ferrofluid-doped lyotropic mesophases: deviation from the Beer-Lambert law.

In this paper is reported a systematic experimental study of the linear-optical-absorption coefficient of ferrofluid-doped isotropic lyotropic mixtures as a function of the magnetic-grains concentration. The linear optical absorption of ferrolyomesophases increases in a nonlinear manner with the concentration of magnetic grains, deviating from the usual Beer-Lambert law. This behavior is associated to the presence of correlated micelles in the mixture which favors the formation of small-scale aggregates of magnetic grains (dimers), which have a higher absorption coefficient with respect to that of isolated grains. We propose that the indirect heating of the micelles via the ferrofluid grains (hyperthermia) could account for this nonlinear increase of the linear-optical-absorption coefficient as a function of the grains concentration.

Behavior of the nonlinear refractive indices and birefringence in the neighborhood of first- and second-order phase transitions in lyotropic liquid crystals.

We investigated the behavior of the nonlinear refractive indices (n(2)) and birefringence (Delta n(2)) in the vicinity of the nematic-to-isotropic (N-I) and nematic uniaxial-to-nematic biaxial (N-N) phase transitions in a lyotropic liquid crystal. The single-beam Z-scan technique is used to measure n(2) in different relative configurations of the electric field of the laser beam and the symmetry axes of the phases. In the N-I transition, the nonlinear optical birefringence shows a discontinuity at the transition temperature (T(c)), as observed in the linear birefringence. On the other hand, in the N-N transition, Delta n(2) was shown to be proportional to /T-T(c)/(-beta), with beta approximately 0.5, in both uniaxial and biaxial nematic domains. No discontinuity was observed on Delta n(2) in the N-N transition. The symmetric invariants of the order parameter were shown to be linear functions of the temperature in the uniaxial nematic domain, in good agreement with the mean-field prediction.

Nanophase segregation of nonpolar solvents in smectic liquid crystals of bent-shape molecules.

Electro-optical, calorimetric, x-ray, and dielectric measurements are reported on a mixture containing a bent-core liquid crystal 4-chloro-1,3-phenylinebis [4-(4-n-tetradecyloxyphenyliminomethyl) benzoate] mixed with the nonpolar solvent n-hexadecane (HEX). It is observed that the addition of HEX depresses the isotropic-to-smectic phase transition temperature, but the crystallization temperature does not change considerably. Instead, the texture of the crystalline phase changes and, at sufficiently high concentrations of HEX (>20 wt %), an optically isotropic phase appears. Above 40 wt % HEX concentrations, the mesophase completely disappears and a direct isotropic solid-to-isotropic liquid transition takes place. At increasing HEX concentration, the transition enthalpies, the layer ordering, and the magnitude of the electric polarization decrease. X-ray studies reveal that HEX molecules pack in between the smectic layers, resulting in an increase of the layer spacing by about 3 A. The increase of the layer spacing saturates at 5 wt % of HEX. The phase segregation observed seems to be due to steric interactions between the flexible HEX molecules and the rigid bent cores of the liquid crystal molecules.

Slow molecular dynamics of water in a lyotropic complex fluid studied by deuterium conventional and spin-lattice relaxometry NMR.

A nuclear magnetic resonance study of protons and deuterons in the mesomorphic phases of the micellar lyotropic mixture potassium laurate/1-decanol/heavy water is reported. The slow dynamical behavior of water molecules has been investigated with deuterons spin-lattice relaxation dispersion in the Larmor frequency range 10(3)