PubMed Health⌕ Search

Biomedical subjects

R C Salvarezza

Publications and source records attributed to R C Salvarezza.

12 recordsLinked to original sources

Evidence for the formation of different energetically similar atomic structures in Ag(111)-(square root[7] x square root[7])-R19.1 degrees-CH3S.

The atomic structure and thermodynamic stability of Ag(111)(sqrt[7]xsqrt[7])-R19.1 degrees -CH3S has been studied by means of density functional calculations and atomistic first principles thermodynamics. The unreconstructed model and two recently proposed reconstructions have been considered. It is found that, in spite of significant differences in the atomic structure, the different surface models have a very similar surface free energy. It is claimed that the different ordered phases can coexist and that the appearance of one or another depends on the external preparation conditions.

Journal Article↗

Complex surface dynamics during anodic dissolution of Ni.

The evolution of the surface roughness during the anodic dissolution of polycrystalline Ni was investigated by means of ex situ AFM in acid phosphate solutions. To characterize the time and spatial scaling behavior of surface roughness, the interface width and the power spectral density of the surface at different dissolution stages were analyzed in terms of dynamic scaling theories. The time dependence of global surface roughness, W(L,t), shows an unstable behavior characterized by a continuous increase without saturation following the relation W approximately t(beta), where beta > 0.5. The unstable behavior results from the development of wide grooves that originates a surface consisting of mounds. Two scaling regimes at scales shorter and larger than the mound dimensions (l(c)) were observed. For l < l(c), we found alpha approximately 1 consistent with mounds exhibiting smooth (faceted) walls, whereas an anomalous scaling behavior with a proper local roughness exponents (alpha(loc) < 1) dominates at l > l(c). The introduction of nitrite in the solution, a common additive used in phosphating baths, leads to some changes in the scaling behavior as a consequence of different generated chemical surface conditions during dissolution. The different dissolution rates of the exposed crystal orientations and surface diffusion of adatoms were identified as the physical processes that govern the interface dynamic for this system.

Journal Article↗

Self-assembled monolayers of alkanethiols on Au(111): surface structures, defects and dynamics.

The surface structures, defects and dynamics of self-assembled monolayers (SAMs) on Au(111) are reviewed. In the case of the well-known c(4 x 2) and radical 3 x radical 3 R30 degrees surface structures, the present discussion is centered on the determination of the adsorption sites. A more complex scenario emerges for the striped phases, where a variety of surface structures that depends on surface coverage are described. Recently reported surface structures at non-saturation coverage show the richness of the self-assembly process. The study of surface dynamics sheds light on the relative stability of some of these surface structures. Typical defects at the alkanethiol monolayer are shown and discussed in relation to SAMs applications.

Gold↗

Role of surface heterogeneity and molecular interactions in the charge-transfer process through self-assembled thiolate monolayers on Au(111).

A comparative study of charge-transfer processes from/to methyl-terminated and carboxylate-terminated thiolate-covered Au(111) surfaces to/from immobilized methylene blue (MB) molecules is presented. Scanning tunneling microscopy images with molecular resolution reveal the presence of molecular-sized defects, missing rows, and crystalline domains with different tilts that turn the thickness of the alkanethiolate SAM (the spacer) uncertain. The degree of surface heterogeneity at the SAMs increases as the number of C units (n) in the hydrocarbon chain decreases from n = 6. Defective regions act as preferred paths for MB incorporation into the methyl-terminated SAMs, driven by hydrophobic forces. The presence of negative-charged terminal groups at the SAMs reduces the number of molecules that can be incorporated, immobilizing them at the outer plane of the monolayer. Only MB molecules incorporated into the SAMs close to the Au(111) surface (at a distance < 0.5 nm) are electrochemically active. MB molecules trapped in different defects explain the broad shape and humps observed in the voltammogram of the redox couple. The heterogeneous charge-transfer rate constants for MB immobilized into methyl-terminated thiolate SAMs are higher than those estimated for carboxylate- terminated SAMs, suggesting a different orientation of the immobilized molecule in the thiolate environment.

Journal Article↗

Influence of the adsorption of N species on the anodic dissolution of Ni.

The dissolution and passivation of Ni in nitrite-containing acid solutions are investigated by Auger spectroscopy, atomic force microscopy, and conventional electrochemical techniques. The dissolution/ passivation of the Ni surface is consistent with a competition between adsorbed OH- and nitrogen-containing species with a potential-dependent surface coverage. Nitrogen-containing species hinder the passivation of the Ni surface, shifting the formation of the complex nickel hydroxide/oxide film to more positive potential values. The dynamics of the dissolving interface, followed by atomic force microscopy, reflect first the competition of adsorbed species, leading to the development of protrusions and cavities, and finally the formation of the passive film that promotes surface smoothening by a preferential dissolution of the protrusion tips under ohmic control.

Journal Article↗

Following adsorption kinetics at electrolyte/metal interfaces through crystal truncation scattering: sulfur on Au(111).

Combining electrochemical methods, in situ scanning tunneling microscopy, and surface x-ray diffraction allowed study of the structure and kinetics of S/Au(111) electrodes in aqueous electrolytes under potential control. Integrated intensities of a particular crystal truncation rod at anti-Bragg conditions were used to trace the sulfur adsorption and desorption as a function of electrode potential in real time. The S desorption is a first order process and the adsorption follows a Langmuir isotherm. A weakly bound S layer is found on the surface before charge transfer, and then specific adsorption occurs.

Journal Article↗

Interface dynamics for copper electrodeposition: the role of organic additives in the growth mode.

An atomistic model for Cu electrodeposition under nonequilibrium conditions is presented. Cu electrodeposition takes place with a height-dependent deposition rate that accounts for fluctuations in the local Cu2+ ions concentration at the interface, followed by surface diffusion. This model leads to an unstable interface with the development of protrusions and grooves. Subsequently the model is extended to account for the presence of organic additives, which compete with Cu2+ for adsorption at protrusions, leading to a stable interface with scaling exponents consistent with those of the Edwards-Wilkinson equation. The model reproduces the interface evolution experimentally observed for Cu electrodeposition in the absence and in the presence of organic additives.

Journal Article↗

Stability analysis of branched silver electrodeposits: solid phase growth under a marginally stable regime.

The mass-transport controlled growth of silver deposits at the early stage of multiple bump formation, and when a silver single needle growth regime is attained, are investigated. Linear stability analysis as proposed by Barkey, Muller, and Tobias [J. Electrochem. Soc. 136, 2199 (1989)] is applied to kinetic mesoscale data. A reasonable correlation between the current density and the average amplitude of unstable perturbation is established.

Journal Article↗

Electrochemical study of endodontic silver cones used in root canal therapy.

In previous studies it was observed that endodontic silver cones placed in fine canals became dislodged as a result of corrosion. To investigate the corrosion of high purity silver, potentiostatic and potentiodynamic electrochemical techniques were used. Triangular potential sweeps made in physiological solutions and human plasma showed similar potential-current relationships. However, in human plasma, peak currents were lower and peak potentials were more anodic than those observed in the physiological solutions. The electron microprobe analysis and the EDAX of the film formed in the biological fluids revealed the presence of silver and chloride and a certain amount of carbon. The addition of small quantities of Na2S to the physiological solutions favoured metal dissolution and promoted the formation of a mixed film of AgCL and Ag2S. According to these results chloride and sulphide anions seem to be particularly aggressive towards the metal surface in implanted silver cones. Precautions to avoid direct contact of the cones with saliva and tissue fluids must be taken. Fractures and discontinuities present in the cement considerably increase the corrosion risks.

Electrochemistry↗

Immunofixation on cellulose acetate: an improved screening method for monoclonal immunoglobulins.

A rapid, simple and economical method is described for typing monoclonal immunoglobulins. It is a modification of the immunofixation electrophoresis method and cellulose acetate has been used as a supporing medium. It involves an initial electrophoretic separation followed by an antigen (Ag)-antibody (Ab) reaction 'in situ'. Eight samples can be typed on each 5.7 cm x 10.5 cm strip and only 20 microliter of commercial antiserum are required (about 2.5 microliter per sample). The method permits detection of monoclonal proteins at concentrations as low as 100 ng/microliter in only 60 min.

Antigen-Antibody Reactions↗

Electrochemical behavior of aluminum in human plasma.

The electrochemical behavior of aluminum in isotonic saline solutions, citrated human plasma, and citrated human blood is studied using potentiostatic and potentiodynamic polarization techniques complemented with scanning electron microscopy (SEM) and dispersive x-ray analysis. The effect of corrosion products on plasmatic proteins is investigated using electron microprobe analysis and immunoelectrophoresis analysis. Electrochemical data show a breakdown of the protective film on aluminium, due to the action of chloride, leading to the pitting of the metal. During pitting, the interaction of aluminium ion and the plasma proteins produces a nonadherent precipitate. Strong protein denaturation can be observed by immunoelectrophoresis of the precipitate suspended in physiologic solutions. The convenience of using organic fluids in addition to saline solutions to evaluate in vitro the behavior of metal for implants is suggested.

Aluminum↗

Study of the biological films formed during the pitting of aluminium in human plasma.

Film formation during the pitting corrosion of aluminium in human plasma is studied using conventional electrochemical techniques complemented with scanning electron microscopy as well as energy-dispersive x-ray, electron microprobe and immunoelectrophoresis analysis. The anodic polarization curve of aluminium in human plasma at 37 degrees C shows a passive region related to a low corrosion rate that extends up to -0.66 V (s.c.e.). At more positive potential values than -0.66 V, the breakdown of the oxide protective film occurs due to the chloride anions, leading to an intense localized dissolution of the metal (pitting corrosion). Scanning electron microscopy of the metal surface reveals a thick non-adherent precipitate covering pits of a crystallographic feature. Energy-dispersive x-ray and the microprobe analysis show the presence of aluminium, chloride and carbon signals. Immunoelectrophoresis of the precipitate resuspended in physiological solution shows a strong protein denaturization. Results suggest that the corrosion products are formed during pitting by the interaction of the saturated AlCl3 salt present within the pits and the adsorbed plasma proteins.

Aluminum↗