Nonlinear behavior of the impedance spectrum of a kerosene based ferrofluid.

We investigate the nonlinear behavior of the electric impedance of a kerosene-based ferrofluid (FF) sample subjected to an ac electric voltage of amplitude ranging from 10 mV to 3 V in the frequency range 6.3 mHz, 100 kHz. The FF sample was inserted between two parallel gold electrodes separated by 127 µm distance. The results show that even a sinusoidal voltage of amplitude low as 80 mV can give origin to nonlinear effects for frequency of the applied voltage smaller than 100 mHz. Our experimental data confirm the results obtained by solving numerically the equations of the Poisson-Nernst-Planck model. From this agreement it follows that the model based on the equation of continuity for the mobile ions, and the equation of Poisson for the actual potential across the sample, works well also in its non-linear version.

Ions, adsorption and electric response of a ferrofluid cell.

We show that the electric response of a cell in the shape of a slab containing a ferrofluid (magnetic particles in kerosene) can be interpreted by means of a model based on the adsorption of ions from limiting surfaces. We report on three samples, identical in all aspects, but limited by electrodes in gold, platinum and titanium. For frequency larger than 1 kHz, the spectra of the real and imaginary parts of the total electrical impedance of the cells are identical. From this result it follows that in this frequency range the response of the cell is independent of the electrodes, which can be considered as blocking. In the low frequency region, up to 0.3 mHz, the response of the cells depends on the electrodes, as discussed recently by Batalioto et al., Phys. Chem. Chem. Phys., 2021, 23, 2819. A simple generalization of the PNP model with ohmic boundary conditions works well only up to 10 mHz. For frequencies smaller than this value the reactance of the cells tends to increase again, indicating a capacity behaviour that could be related to the adsorption effect of the electrodes. A generalization of the ohmic PNP model containing surface capacitance in series is able to fit the data. From the value of the surface capacitance, the thickness of the surface layer is estimated to be on the molecular scale. From this result, we conclude that the adsorption phenomenon could be important for the description of the electrical properties of these systems. A simple generalization of the PNP model with boundary conditions derived by the Langmuir model is in reasonable agreement with our experimental data. The analysis is performed at the impedance level, taking into account a test based on the tangent of the loss angle of the system.

Influence of nanoparticle size on the nonlinear optical properties of magnetite ferrofluids.

The nonlinear index of refraction (n_{2}) and the two-photon absorption coefficient (ß) of water-based ferrofluids made of magnetite nanocrystals of different sizes and with different coatings have been measured through the Z-scan technique, with ultrashort (femtoseconds) laser pulses. Their third-order susceptibility is calculated from the values of n_{2} and ß. The influence of different particles' coatings and sizes on these nonlinear optical properties are investigated. The values of n_{2} and ß depend more significantly on the nanoparticles' size than on the particular coating. We observe a decrease of ß as the nanoparticles' diameters decrease, although the optical gap is found to be the same for all samples. The results are interpreted considering modifications in the electronic orbital shape due to the particles' nanosize effect.

Cu and Fe metallic ions-mediated oxidation of low-density lipoproteins studied by NMR, TEM and Z-scan technique.

In this work we report on a study of the morphological changes of LDL induced in vitro by metallic ions (Cu(2+) and Fe(3+)). These modifications were characterized by transmission electron microscopy, nuclear magnetic resonance and the Z-scan technique. The degree of oxidative modification of LDL was determined by the TBARS and lipid hydroperoxides assays. It is shown that distinct pathways for modifying lipoproteins lead to different morphological transformations of the particles characterized by changes in size and/or shape of the resulting particles, and by the tendency to induce aggregation of the particles. There were no evidence of melting of particles promoted by oxidative processes with Cu and Fe.

Enhancement on the Europium emission band of Europium chlortetracycline complex in the presence of LDL.

Low-density lipoprotein (LDL) particles are the major cholesterol-carrying lipoprotein in the human circulation from the liver to peripheral tissues. High levels of LDL-Cholesterol (LDL-C) are known risk factor for the development of coronary artery disease (CAD). The most common approach to determine the LDL-C in the clinical laboratory involves the Friedewald formula. However, in certain situations, this approach is inadequate. In this paper we report on the enhancement on the Europium emission band of Europium chlortetracycline complex (CTEu) in the presence of LDL. The emission intensity at 615 nm of the CTEu increases with increasing amounts of LDL. This phenomenon allowed us to propose a method to determine the LDL concentration in a sample composed by an aqueous solution of LDL. With this result we obtained LDL calibration curve, LOD (limit of detection) of 0.49 mg/mL and SD (standard deviation) of 0.003. We observed that CTEu complex provides a wider dynamic concentration-range for LDL determination than that from Eu-tetracycline previously. The averaged emission lifetimes of the CTEu and CTEu with LDL (1.5 mg/mL) complexes were measured as 15 and 46 micros, respectively. Study with some metallic interferents is presented.

Characterization of native and oxidized human low-density lipoproteins by the Z-scan technique.

The nonlinear optical response of human normal and oxidized by Cu2+ low-density lipoproteins particles (LDL), were investigated by the Z-scan technique as a function of temperature and concentration of LDL particles. The Z-scan signals increase linearly with concentration of normal LDL particles, following the usual Beer-Lambert law in a broad range of concentrations. The oxidized LDL particles do not show nonlinear optical response. On the other hand, normal LDL increases its nonlinear optical response as a function of temperature. These behaviors can be attributed to an absorbing element that is modified by the oxidative process. Contrarily, changes in the physical state of the cores and conformation of the ApoB100 protein due to an increase in temperature seems to enhance their nonlinear optical properties. This tendency is not due to aggregation of particles. The main contribution to the nonlinear optical response of normal LDL particles comes from the phospholipid fraction of the particles.