Smart Plastic Antibody Material for Hemoglobin Tailored by Silica Surface Imprinting and with Charged Binding Sites: Its use as Ionophore in Potentiometric Transduction

JORNADAS DE ELECTROQUÍMICA E INOVAÇÃO 2013Human hemoglobin (Hb) is a globular metalloprotein, present in the blood and involved in gas transport. Hb-associated disturbances are related to several diseases, such thalassemia, anemia, heart disease and leukemia, or to side-effects from other diseases, such as cancer. Overall, it is of great importance to know the concentration of Hb in the blood in many health-related conditions. There are many methods described in the literature for determining Hb. Most of these rely on antibody/antigen interactions, due to the high selectivity of the affinity reaction taking place between these biomolecules. However, the use of antibodies for Hb determination in routine clinical use is very expensive, due to the high cost of the material, the need for special handling and storage, and the non-reusability. These constraints may be limited by replacing natural antibodies by plastic receptors, obtained by molecular imprinting procedures. Thus, this work describes a novel smart plastic antibody material (SPAM) by surface imprinting technique for the detection of Hb and its application to design small, portable and low cost potentiometric devices. The SPAM material was obtained by linking Hb to silica nanoparticles and allowing its subsequent interaction with different vinyl monomers, of different chemical functions and ionic charges. Control materials were designed in parallel to assess the ability of establishing stereochemical recognition of Hb and the effect of the kind/charge of the monomers employed. Scanning Electron Microscopy analysis confirmed the surface modification of the silica material used for imprint. All materials were mixed with PVC/plasticizer and applied as selective membranes in potentiometric transduction. Suitable emf variations were detected only for selective membranes having a SPAM material and a charged lipophilic anionic additive. All control materials were unable to produce a potentiometric response. Overall, good features were obtained for SPAM-based selective membranes carrying an anionic lipophilic additive. In HEPES buffer of pH 5, limits of detection were 43.8μg/mL for a linear response after 83.8μg/mL with a cationic slope of +40.4mV/decade. Good selectivity was also observed against other coexisting biomolecules. The analytical application was conducted successfully, showing accurate and precise results

Thermostatistics of overdamped motion of interacting particles

We show through a nonlinear Fokker-Planck formalism, and confirm by molecular dynamics simulations, that the overdamped motion of interacting particles at T=0, where T is the temperature of a thermal bath connected to the system, can be directly associated with Tsallis thermostatistics. For sufficiently high values of T, the distribution of particles becomes Gaussian, so that the classical Boltzmann-Gibbs behavior is recovered. For intermediate temperatures of the thermal bath, the system displays a mixed behavior that follows a novel type of thermostatistics, where the entropy is given by a linear combination of Tsallis and Boltzmann-Gibbs entropies.Comment: 4 pages, 2 figure

Spin-Electron-Phonon Excitation in Re-based Half-Metallic Double Perovskites

A remarkable hardening (~ 30 cm-1) of the normal mode of vibration associated with the symmetric stretching of the oxygen octahedra for the Ba2FeReO6 and Sr2CrReO6 double perovskites is observed below the corresponding magnetic ordering temperatures. The very large magnitude of this effect and its absence for the anti-symmetric stretching mode provide evidence against a conventional spin-phonon coupling mechanism. Our observations are consistent with a collective excitation formed by the combination of the vibrational mode with oscillations of local Fe or Cr 3d and Re 5d occupations and spin magnitudes.Comment: 12 pages, 4 figure

Dynamical reentrance and geometry imposed quantization effects in Nb-AlOx-Nb Josephson junction arrays

In this paper, we report on different phenomena related to the magnetic properties of artificially prepared highly ordered (periodic) two-dimensional Josephson junction arrays (2D-JJA) of both shunted and unshunted Nb-AlOx-Nb tunnel junctions. By employing mutual-inductance measurements and using a high-sensitive bridge, we have thoroughly investigated (both experimentally and theoretically) the temperature and magnetic field dependence of complex AC susceptibility of 2D-JJA. We also demonstrate the use of the scanning SQUID microscope for imaging the local flux distribution within our unshunted arrays

Invasion Percolation Between two Sites

We investigate the process of invasion percolation between two sites (injection and extraction sites) separated by a distance r in two-dimensional lattices of size L. Our results for the non-trapping invasion percolation model indicate that the statistics of the mass of invaded clusters is significantly dependent on the local occupation probability (pressure) Pe at the extraction site. For Pe=0, we show that the mass distribution of invaded clusters P(M) follows a power-law P(M) ~ M^{-\alpha} for intermediate values of the mass M, with an exponent \alpha=1.39. When the local pressure is set to Pe=Pc, where Pc corresponds to the site percolation threshold of the lattice topology, the distribution P(M) still displays a scaling region, but with an exponent \alpha=1.02. This last behavior is consistent with previous results for the cluster statistics in standard percolation. In spite of these discrepancies, the results of our simulations indicate that the fractal dimension of the invaded cluster does not depends significantly on the local pressure Pe and it is consistent with the fractal dimension values reported for standard invasion percolation. Finally, we perform extensive numerical simulations to determine the effect of the lattice borders on the statistics of the invaded clusters and also to characterize the self-organized critical behavior of the invasion percolation process.Comment: 7 pages, 11 figures, submited for PR

A novel antibody-like material for breast cancer antigen CA15-3, used to track breast cancer by potentiometric transduction

This work presents the development of a low cost sensor device for the diagnosis of breast cancer in point-of-care, made with new synthetic biomimetic materials inside plasticized poly(vinyl chloride), PVC, membranes, for subsequent potentiometric detection. This concept was applied to target a conventional biomarker in breast cancer: Breast Cancer Antigen (CA15-3). The new biomimetic material was obtained by molecularly-imprinted technology. In this, a plastic antibody was obtained by polymerizing around the biomarker that acted as an obstacle to the growth of the polymeric matrix. The imprinted polymer was specifically synthetized by electropolymerization on an FTO conductive glass, by using cyclic voltammetry, including 40 cycles within -0.2 and 1.0 V. The reaction used for the polymerization included monomer (pyrrol, 5.0×10-3 mol/L) and protein (CA15-3, 100U/mL), all prepared in phosphate buffer saline (PBS), with a pH of 7.2 and 1% of ethylene glycol. The biomarker was removed from the imprinted sites by proteolytic action of proteinase K. The biomimetic material was employed in the construction of potentiometric sensors and tested with regard to its affinity and selectivity for binding CA15-3, by checking the analytical performance of the obtained electrodes. For this purpose, the biomimetic material was dispersed in plasticized PVC membranes, including or not a lipophilic ionic additive, and applied on a solid conductive support of graphite. The analytical behaviour was evaluated in buffer and in synthetic serum, with regard to linear range, limit of detection, repeatability, and reproducibility. This antibody-like material was tested in synthetic serum, and good results were obtained. The best devices were able to detect 5 times less CA15-3 than that required in clinical use. Selectivity assays were also performed, showing that the various serum components did not interfere with this biomarker. Overall, the potentiometric-based methods showed several advantages compared to other methods reported in the literature. The analytical process was simple, providing fast responses for a reduced amount of analyte, with low cost and feasible miniaturization. It also allowed the detection of a wide range of concentrations, diminishing the required efforts in previous sample pre-treating stages