Protein Assembly onto Cationic Supported Bilayers

Cationic supported bilayers on latex are useful to isolate and immobilize oppositely charged proteins as a monomolecular layer over a range of low protein concentrations and particle number densities. Cholera toxin (CT) from Vibrio cholerae, an 87 kDa AB(5) hexameric protein and bovine serum albumin (BSA) self-assembled on dioctadecyldimethylammonium bromide (DODAB) supported bilayers with high affinity yielding highly organized and monodisperse particulates at 5 x 10(9) particles/mL, over a range of low protein concentrations (0-0.025 mg/mL BSA or CT). Protein association onto the bilayer-covered polystyrene sulfate (PSS) was determined from adsorption isotherms, dynamic light scattering for size distributions and zeta-potential analysis revealing a monomolecular, thin and highly organized protein layer surrounding each particle with potential for biospecific recognition such as antigen-antibody, receptor-ligand, hybridization of oligonucleotide sequences, all of them important in immunodiagnosis, selective biomolecular chromatographic separations, microarrays design and others.

Chemical modification of a nanocrystalline TiO(2) film for efficient electric connection of glucose oxidase

A novel biosensor for glucose was prepared by adsorption of 1,1`-bis(4-carboxybenzyl)-4,4`-bipyridinium di-bromide compound (H(2)BpybcBr(2)) onto the surface of a nanocrystalline TiO(2) film deposited onto FTO glasses, which was used as a platform to assemble the enzyme glucose oxidase to the electrode surface. The H(2)BpybcBr(2)/TiO(2)/FTO modified electrode was characterized by scanning electron microscopy, X-ray fluorescence image, cyclic voltammograms and spectroelectrochemical measurements. The immobilization of GOD on functionalized TiO(2) film led to stable amperometric biosensing for glucose with a linear range from 153 mu mol L(-1) to 1.30 mmol L(-1) and a detection limit of 51 mu mol L(-1). The apparent Michaelis-Menten constant (K(m)) was estimated to be 3.76 mmol L(-1), which suggested a high enzyme-substrate affinity. The maximum electrode sensitivity was 1.25 mu A mmol L(-1). The study proved that the combination of viologen mediators with TiO(2) film retains the electrocatalytic activity of the enzyme, and also enhances the electron transfer process, and hence regenerating the enzyme in the reaction with glucose. (C) 2010 Elsevier Inc. All rights reserved.

Lithium Ion Electro-Insertion and Spectroelectrochemical Properties of Films from Hexaniobate

Layer-by-layer (LbL) films from K(2)Nb(6)O(17)(2-) and polyallylamine (PAH) and dip-coating films of H(2)K(2)Nb(6)O(17) were prepared on a fluorine-doped tin-oxide (FTO)-coated glass. The atomic force microscopy (AFM) images were carried out for morphological characterization of both materials. The real surface area and the roughness factor were determined on the basis of pseudocapacitive processes involved in the electroreduction/electrooxidation of gold layers deposited on these films. Next, lithium ion insertion into these materials was examined by means of electrochemical and spectroelectrochemical measurements. More specifically, cyclic voltammetry and current pulses under visible light beams were used to investigate mass transport and chromogenic properties. The lithium ion diffusion coefficient (D(Li)) within the LbL matrix is significantly higher than that within the dip-coating film, ensuring high storage capacity of lithium ions in the self-assembled electrode. Contrary to the LbL film, the potentiodynamic profile of absorbance change (Delta A) as a function of time is not similar to that obtained in the case of current density for the dip-coating film. Aiming at analyzing the rate of the coloration front associated with lithium ion diffusion, a spectroelectrochemical method based on the galvanostatic intermittent titration technique (GITT) was employed so as to determine the ""optical"" diffusion coefficient (D(op)). In the dip-coating film, the method employed here revealed that the lithium ion rate is higher in diffusion pathways formed from K(2)Nb(6)O(17)(2-) sites that contribute more significantly to Delta A. Meanwhile, the presence of PAH contributed to the increased ionic mobility in diffusion pathways in the LbL film, with low contribution to the electrochromic efficiency. These results aided a better understanding of the potentiodynamic profile of the temporal change of absorbance and current density during the insertion/deinsertion of lithium ions into the electrochromic materials.

Supramolecular Approach to Gold Nanoparticle/Triruthenium Cluster Hybrid Materials and Interfaces

A systematic and comprehensive study of the interaction of citrate-stabilized gold nanoparticles with triruthenium cluster complexes of general formula [Ru(3)(CH(3)COO)(6)(L)](+) [L = 4-cyanopyridine (4-CNpy), 4,4`-bipyridine (4,4`-bpy) or 4,4`-bis(pyridyl)ethylene (bpe)] has been carried out. The cluster-nanoparticle interaction in solution and the construction of thin films of the hybrid materials were investigated in detail by electronic and surface plasmon resonance (SPR) spectroscopy, Raman scattering spectroscopy and scanning electron microscopy (SEM). Citrate-stabilized gold nanoparticles readily interacted with [Ru(3)O(CH(3)COO)(6)(L)(3)](+) complexes to generate functionalized nanoparticles that tend to aggregate according to rates and extents that depend on the bond strength defined by the characteristics of the cluster L ligands following the sequence bpe > 4,4`-bpy >> 4-CNpy. The formation of compact thin films of hybrid AuNP/[Ru(3)O(CH(3)COO)(6)(L)(3)](+) derivatives with L = bpe and 4,4`-bpy indicated that the stability/lability of AuNP-cluster bonds as well as their solubility are important parameters that influence the film contruction process. Fluorine-doped tin oxide electrodes modified with thin films of these nanomaterials exhibited similar electrocatalytic activity but much higher sensitivity than a conventional gold electrode in the oxidation of nitrite ion to nitrate depending on the bridging cluster complex, demonstrating the high potential for the development of amperometric sensors.

Physical Vapor Deposited Thin Films of Lignins Extracted from Sugar Cane Bagasse: Morphology, Electrical Properties, and Sensing Applications

The concern related to the environmental degradation and to the exhaustion of natural resources has induced the research on biodegradable materials obtained from renewable sources, which involves fundamental properties and general application. In this context, we have fabricated thin films of lignins, which were extracted from sugar cane bagasse via modified organosolv process using ethanol as organic solvent. The films were made using the vacuum thermal evaporation technique (PVD, physical vapor deposition) grown up to 120 nm. The main objective was to explore basic properties such as electrical and surface morphology and the sensing performance of these lignins as transducers. The PVD film growth was monitored via ultraviolet-visible (UV-vis) absorption spectroscopy and quartz crystal microbalance, revealing a linear relationship between absorbance and film thickness. The 120 nm lignin PVD film morphology presented small aggregates spread all over the film surface on the nanometer scale (atomic force microscopy, AFM) and homogeneous on the micrometer scale (optical microscopy). The PVD films were deposited onto Au interdigitated electrode (IDE) for both electrical characterization and sensing experiments. In the case of electrical characterization, current versus voltage (I vs V) dc measurements were carried out for the Au IDE coated with 120 nm lignin PVD film, leading to a conductivity of 3.6 x 10(-10) S/m. Using impedance spectroscopy, also for the Au IDE coated with the 120 nm lignin PVD film, dielectric constant of 8.0, tan delta of 3.9 x 10(-3)) and conductivity of 1.75 x 10(-9) S/m were calculated at 1 kHz. As a proof-of-principle, the application of these lignins as transducers in sensing devices was monitored by both impedance spectroscopy (capacitance vs frequency) and I versus time dc measurements toward aniline vapor (saturated atmosphere). The electrical responses showed that the sensing units are sensible to aniline vapor with the process being reversible. AFM images conducted directly onto the sensing units (Au IDE coated with 120 nm lignin PVD film) before and after the sensing experiments showed a decrease in the PVD film roughness from 5.8 to 3.2 nm after exposing to aniline.

Layer by layer TiO2 thin films and photodegradation of Congo red

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Two-colour photocurrent detection technique for coherent control of a single InGaAs/GaAs quantum dot

We present a two-colour photocurrent detection method for coherent control of a single InGaAs/GaAs self-assembled quantum dot. A pulse shaping technique provides a high degree of control over picosecond optical pulses. Rabi rotations on the exciton to biexciton transition are presented, and fine structure beating is detected via time-resolved measurements. (c) 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Towards coherent optical control of a single hole spin: Rabi rotation of a trion conditional on the spin state of the hole

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

In situ evaluation of anticancer drug methotrexate-DNA interaction using a DNA-electrochemical biosensor and AFM characterization

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

The role of pressure in the electrical transport of doped plasticized polyanilines

The behaviour of dc longitudinal and transverse conductivity in self-assembled plastdoped films of polyaniline has been studied over the range of 9 K to 320 K, under different applied mechanical pressures. We observe a progressive evolution of the conductivity picture as the applied pressure is increased, especially in the transverse direction, where the conductivity tends to lower as the pressure is increased. (C) 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

On the reversed crystal growth of BaZrO3 decaoctahedron: shape evolution and mechanism

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Radio luminescence properties of decaoctahedral BaZrO3

Radioluminescence (RL) emissions were obtained for the BaZrO3 self-assembled nanocrystals under decaoctahedral shape, if produced via microwave-assisted hydrothermal method. Trapped F centers created within the band gap are the result of order-disorder effects, which act as key factors supporting significant RL emission through a detrapping process. The influences of size and morphology on RL properties are take into account. No radiation damage or loss of emission intensity was observed. (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Supramolecular assemblies of cis-palladium complexes dominated by C-H center dot center dot center dot Cl interactions

Two cis-related palladium(II) complexes [PdCl(2)(PPh(3))(tu)] (1) and [PdCl(2)(tmen)] (2) {PPh(3) = triphenylphosphine, tu = thiourea, tmen = N,N,N,N-tetramethylethylenediamine} have been synthesized and characterized by elemental analysis, IR and NMR spectroscopies, and single crystal X-ray diffraction. In 1, N-H center dot center dot center dot Cl hydrogen bonds are responsible for the formation of a dimer which connects to an adjacent one through weak C-H center dot center dot center dot Cl interactions, yielding 1D tapes. The crystal packing of compound 2 consists of zigzag ribbons of [PdCl(2)(tmen)] self-assembled by C-H center dot center dot center dot Cl hydrogen bonds which also holds the chains together, giving rise to a 2D layered structure. (C) 2006 Elsevier B.V. All rights reserved.

Studies on the interaction between humic substances and conducting polymers for sensor application

The interaction between humic substances and poly(o-ethoxyaniline) (POEA), a conducting polymer, was investigated for both solution and self-assembled films. The results have shown that the humic substances induce a doping of POEA by protonation, as indicated by UV-Vis and Raman spectroscopies. The atomic force microscopy (AFM) studies on the self-assembled films have shown that the average roughness of the polymer film has increased after exposing it to humic substances (fulvic and humic acids), consistent with the interaction between POEA and humic substances. However, this change in morphology is reversible by washing the films with water in agreement with the electrical data allowing using this system in sensor applications. Here, the sensor formed by an array of different sensing units was able to detect and distinguish humic substances in aqueous solution, as shown by multivariate analysis (principal component analysis). The motivation to detect humic substance comes due to its importance in terms of quality control of water or soil. ©2005 Sociedade Brasileira de Química.

Elucidating capacitance and resistance terms in confined electroactive molecular layers

Electrochemical analyses on confined electroactive molecular layers, herein exemplified with electroactive self-assembled monolayers, sample current contributions that are significantly influenced by additional nonfaradaic and uncompensated resistance effects that, though unresolved, can strongly distort redox analysis. Prior work has shown that impedance-derived capacitance spectroscopy approaches can cleanly resolve all contributions generated at such films, including those which are related to the layer dipolar/electrostatic relaxation characteristics. We show herein that, in isolating the faradaic and nonfaradaic contributions present within an improved equivalent circuit description of such interfaces, it is possible to accurately simulate subsequently observed cyclic voltammograms (that is, generated current versus potential patterns map accurately onto frequency domain measurements). Not only does this enable a frequency-resolved quantification of all components present, and in so doing, a full validation of the equivalent circuit model utilized, but also facilitates the generation of background subtracted cyclic voltammograms remarkably free from all but faradaic contributions. © 2012 American Chemical Society.