Polyelectrolyte-protein complexation driven by charge regulation

The interplay between the biocolloidal characteristics (especially size and charge), pH, salt concentration and the thermal energy results in a unique collection of mesoscopic forces of importance to the molecular organization and function in biological systems. By means of Monte Carlo simulations and semi-quantitative analysis in terms of perturbation theory, we describe a general electrostatic mechanism that gives attraction at low electrolyte concentrations. This charge regulation mechanism due to titrating amino acid residues is discussed in a purely electrostatic framework. The complexation data reported here for interaction between a polyelectrolyte chain and the proteins albumin, goat and bovine alpha-lactalbumin, beta-lactoglobulin, insulin, k-casein, lysozyme and pectin methylesterase illustrate the importance of the charge regulation mechanism. Special attention is given to pH congruent to pI where ion-dipole and charge regulation interactions could overcome the repulsive ion-ion interaction. By means of protein mutations, we confirm the importance of the charge regulation mechanism, and quantify when the complexation is dominated either by charge regulation or by the ion-dipole term.

Electrochemical Evidence of Strong Electronic Interaction of PtRu on Carbon Nanotubes with High Density of Defects

We show that carbon nanotubes (CNTs) with high density of defects can present a strong electronic interaction with nanoparticles of Pt-Ru with average particle size of 3.5 +/- 0.8 nm. Depending on the Pt-Ru loading on the CNTs, CO and methanol oxidation reactions suggest there is a charge transfer between Pt-Ru that in turn provokes a decrease in the electronic interaction taking place between Ru and Pt in the PtRu alloy. The CO stripping potentials were observed at about 0.65 and 0.5 V for Pt-Ru/CNT electrodes with Pt-Ru loadings of 10 and 20, and 30 wt %, respectively. (C) 2008 The Electrochemical Society. [DOI: 10.1149/1.2990222] All rights reserved.

High-temperature X-ray powder diffraction study of the tetragonal-cubic phase transition in nanocrystalline, compositionally homogeneous ZrO2-CeO2 solid solutions

Crystal structure of compositionally homogeneous, nanocrystalline ZrO2-CeO2 solutions was investigated by X-ray powder diffraction as a function of temperature for compositions between 50 and 65 mol % CeO2 center dot ZrO2-50 and 60 mol % CeO2 solid solutions, which exhibit the t'-form of the tetragonal phase at room temperature, transform into the cubic phase in two steps: t'-to-t '' followed by t ''-to-cubic. But the ZrO2-65 mol % CeO2, which exhibits the t ''-form, transforms directly to the cubic phase. The results suggest that t'-to-t '' transition is of first order, but t ''-to-cubic seems to be of second order. (C) 2008 International Centre for Diffraction Data.

Synchrotron X-ray powder diffraction study of the tetragonal-cubic phase transition in nanostructured ZrO2-Sc2O3 solid solutions

The transition between tetragonal and cubic phases in nanostructured ZrO2-Sc2O3 solid solutions by high-temperature X-ray powder diffraction using synchrotron radiation is presented. ZrO2-8 and 11 mol% Sc2O3 nanopowders that exhibit the t'- and t ''-forms of the tetragonal phase, respectively, were synthesized by a stoichiometric nitrate-lysine gel-combustion route. The average crystallite size treated at 900 degrees C was about 25 nm for both compositions. Our results showed that t'-t '' and t ''-cubic transitions take place for the 8 and 11 mol% Sc2O3 samples, respectively. (C) 2008 International Centre for Diffraction Data.

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.

Free-standing urethane/urea elastomer films undoped and doped with ferro-nano-particles

We report on an experimental study of the structures presented by urethane/urea elastomeric films without and with ferromagnetic nanoparticles incorporated. The study is made by using the X-ray diffraction, nuclear magnetic resonance (NMR), optical, atomic and magnetic force (MFM) microscopy techniques, and mechanical assays. The structure of the elastomeric matrix is characterized by a distance of 0.46 nm between neighboring molecular segments, almost independent on the stretching applied. The shear casting performed in order to obtain the elastomeric films tends to orient the molecules parallel to the flow direction thus introducing anisotropy in the molecular network which is reflected on the values obtained for the orientational order parameter and its increase for the stretched films. In the case of nanoparticles-doped samples, the structure remains nearly unchanged although the local order parameter is clearly larger for the undoped films. NMR experiments evidence modifications in the molecular network local ordering. Micrometer size clusters were observed by MFM for even small concentration of magnetic particles.

Supramolecular polymorphism of DNA in non-cationic L(alpha) lipid phases

The structure of a complex between hydrated DNA and a non-cationic lipid is studied, including its phase diagram. The complex is spontaneously formed by adding DNA fragments (ca. 150 base pairs in length) to non-cationic lipids and water. The self-assembly process often leads to highly ordered structures. The structures were studied by combining X-ray scattering, fluorescence and polarized microscopy, as well as freeze-fracture experiments with transmission electron microscopy. We observe a significant increase of the smectic order as DNA is incorporated into the water layers of the lamellar host phase, and stabilization of single phase domains for large amounts of DNA. The effect of confinement on DNA ordering is investigated by varying the water content, following three dilution lines. A rich polymorphism is found, ranging from weakly correlated DNA-DNA in-plane organizations to highly ordered structures, where transmembrane correlations lead to the formation of columnar rectangular and columnar hexagonal superlattices of nucleotides embedded between lipid lamellae. From these observations, we suggest that addition of DNA to the lamellar phase significantly restricts membrane fluctuations above a certain concentration and helps the formation of the lipoplex. The alteration of membrane steric interactions, together with the appearance of interfacial interactions between membranes and DNA molecules may be a relevant mechanism for the emergence of highly ordered structures in the concentrated regime.

Anisotropic Confinement, Electronic Coupling and Strain Induced Effects Detected by Valence-Band Anisotropy in Self-Assembled Quantum Dots

A method to determine the effects of the geometry and lateral ordering on the electronic properties of an array of one-dimensional self-assembled quantum dots is discussed. A model that takes into account the valence-band anisotropic effective masses and strain effects must be used to describe the behavior of the photoluminescence emission, proposed as a clean tool for the characterization of dot anisotropy and/or inter-dot coupling. Under special growth conditions, such as substrate temperature and Arsenic background, 1D chains of In(0.4)Ga(0.6) As quantum dots were grown by molecular beam epitaxy. Grazing-incidence X-ray diffraction measurements directly evidence the strong strain anisotropy due to the formation of quantum dot chains, probed by polarization-resolved low-temperature photoluminescence. The results are in fair good agreement with the proposed model.

Internal Strain Distribution in Freestanding Porous Silicon

Elastic properties of freestanding porous silicon layers fabricated by electrochemical anodization were studied by Raman scattering. Different anodization currents provided different degrees of porosity in the nanometer scale. Raman lines corresponding to the longitudinal optical phonons of crystalline and amorphous phases were observed. The amorphous volume fraction increased and the phonon frequencies for both phases decreased with increasing porosity. A strain distribution model is proposed whose fit to the experimental results indicates that the increasing nanoscale porosity causes strain relaxation in the amorphous domains and strain buildup in the crystalline ones. The present analysis has significant implications on the estimation of the crystalline Si domain's characteristic size from Raman scattering data. (C) 2009 The Electrochemical Society. [DOI: 10.1149/1.3225832] All rights reserved.

Nanostructured Films Based on Carbon Nanotubes and Cobalt for the Electrocatalytic Reduction of H(2)O(2)

This paper presents the fabrication of a nanothick Co-modified film electrochemically synthesized on layer-by-layer (LbL) structures made with dendrimer polyamidoamine/carbon nanotubes (PAMAM/CNT), and its electrocatalytic properties toward H(2)O(2) reduction. Scanning electron microscopy indicated the formation of a homogeneous, 14 nm thick Co film. The porous nature of the PAMAM/CNT LbL film allowed the electrolyte access to the bottom of the electrode, generating a homogenous Co electrodeposit. In addition, the nanostructure based on Co-modified PAMAM/CNT LbL exhibited high electrocatalytic activity for H(2)O(2) reduction when compared to the Co-free PAMAM/CNT LbL film, which demonstrates the suitability of the system studied for biosensing. (C) 2011 The Electrochemical Society. [DOI: 10.1149/1.3602200] All rights reserved.

Optimized architecture for Tyrosinase-containing Langmuir-Blodgett films to detect pyrogallol

The control of molecular architectures has been a key factor for the use of Langmuir-Blodgett (LB) films in biosensors, especially because biomolecules can be immobilized with preserved activity. In this paper we investigated the incorporation of tyrosinase (Tyr) in mixed Langmuir films of arachidic acid (AA) and a lutetium bisphthalocyanine (LuPc(2)), which is confirmed by a large expansion in the surface pressure isotherm. These mixed films of AA-LuPc(2) + Tyr could be transferred onto ITO and Pt electrodes as indicated by FTIR and electrochemical measurements, and there was no need for crosslinking of the enzyme molecules to preserve their activity. Significantly, the activity of the immobilised Tyr was considerably higher than in previous work in the literature, which allowed Tyr-containing LB films to be used as highly sensitive voltammetric sensors to detect pyrogallol. Linear responses have been found up to 400 mu M, with a detection limit of 4.87 x 10(-2) mu M (n = 4) and a sensitivity of 1.54 mu A mu M(-1) cm(-2). In addition, the Hill coefficient (h = 1.27) indicates cooperation with LuPc(2) that also acts as a catalyst. The enhanced performance of the LB-based biosensor resulted therefore from a preserved activity of Tyr combined with the catalytic activity of LuPc(2), in a strategy that can be extended to other enzymes and analytes upon varying the LB film architecture.

Intermolecular energy transfer and photostability of luminescence-tuneable multicolour PMMA films doped with lanthanide-beta-diketonate complexes

It is reported in this work the preparation, characterisation and photoluminescence study of poly(methylmethacrylate) (PMMA) thin films co-doped with [Eu(tta)(3)(H(2)O)(2)] and [Tb(acac)(3)(H(2)O)(3)] complexes. Both the composition and excitation wavelength may be tailored to fine-tune the emission properties of these Ln(3+)-beta-diketonate doped polymer films, exhibiting green and red primary colours, as well as intermediate colours. In addition to the ligand-Ln(3+) intramolecular energy transfer, it is observed an unprecedented intermolecular energy transfer process from the (5)D(4) emitting level of the Tb(3+) ion to the excited triplet state T(1) of the tta ligand coordinated to the Eu(3+) ion. The PMMA polymer matrix acts as a co-sensitizer and enhances the overall luminescence intensity of the polymer films. Furthermore, it provides considerable UV protection for the luminescent species and improves the photostability of the doped system.

Structural control of gold nanoparticles self-assemblies by layer-by-layer process

This work presents a novel way to introduce gold nanoparticles (Au NPs) in a multilayer polymer produced by the layer-by-layer (LbL) assembling technique. The technique chosen shows that, depending on the pH used, different morphological structures can be obtained from monolayer or bilayer Au NPs. The MEIS and RBS techniques allowed for the modelling of the interface polymer-NPs, as well as the understanding of the interaction of LbL system, when adjusting the pH in weak polyelectrolytes. The process reveals that the optical properties of multilayer systems could be fine-tuned by controlling the addition of metallic nanoparticles, which could also modify specific polarization responses.

Probing magnetic and gold nanoparticles by using MAClevers (R) as ultrasensitive sensors

Magnetic AFM probes known as MAClevers (R) were employed for sensing picogram amounts of magnetic nanoparticles, based on the cantilever frequency shifts resulting from the magnetically induced adsorption of mass. By using organothiol functionalized magnetic nanoparticles, this analytical strategy was successfully extended to the detection of gold nanoparticles, as confirmed by confocal Raman microscopy.

X-ray diffraction data of tibolone Delta(4) isomer (isotibolone)

Tibolone is used for hormone reposition of postmenopause women and isotibolone is considered the major degradation product of tibolone. Isotibolone can also be present in tibolone API raw materials due to some inadequate synthesis. Its presence is then necessary to be identified and quantified in the quality control of both API and drug products. In this work we present the indexing of an isotibolone X-ray diffraction pattern measured with synchrotron light (lambda=1.2407 angstrom) in the transmission mode. The characterization of the isotibolone sample by IR spectroscopy, elemental analysis, and thermal analysis are also presented. The isotibolone crystallographic data are a=6.8066 angstrom, b=20.7350 angstrom, c=6.4489 angstrom, beta=76.428 degrees, V=884.75 angstrom(3), and space group P2(1), rho(o)= 1.187 g cm(-3), Z=2. (C) 2009 International Centre for Diffraction Data. [DOI: 10.1154/1.3257612]