Biomedical subjects

Roberto C Salvarezza

Publications and source records attributed to Roberto C Salvarezza.

13 recordsLinked to original sources

PubMed2007

Electrocatalytic and magnetic properties of ultrathin nanostructured iron-melanin films on Au(111).

We have prepared ultrathin, nanostructured melanin films on Au(111) by means of electrochemical self-assembly. These films were characterized by using Auger electron spectroscopy, X-ray absorption near-edge structure spectroscopy, scanning tunneling microscopy, magnetic force microscopy, and electrochemical techniques. Two types of nanostructures are present in the film: melanin nanoparticles and Fe(3)O(4) nanoparticles. The melanin nanoparticles contain Fe bonded to oxygen-containing phenolic groups in an octahedral configuration similar to that found in Fe(2)O(3). The inorganic-organic composite exhibits magnetic properties and catalyzes the electroreduction of hydrogen peroxide in alkaline and neutral electrolyte solutions. The electrocatalytic activity depends on the Fe-bound melanin and appears to be similar to that found for Fe-porphyrins.

Catalysis↗

PubMed2006

Room-temperature kinetics of short-chain alkanethiol film growth on Ag(111) from the vapor phase.

We have used time-of-flight (TOF) direct recoiling spectroscopy (DRS) to follow propanethiol adsorption at 300 K from the vapor phase on an Ag(111) surface, for exposures ranging from 10(-1) to 10(5) L. Results show that the adsorption proceeds with changes in the sticking coefficient, consistent with at least three phases. At low exposures, the alkanethiol molecules adsorb with high probability at defect sites, followed by a slower growth mode that essentially covers the whole surface. A third change in the sticking coefficient is associated with the final saturation stage, corresponding to a thicker layer related to molecules in a more upright orientation. The adsorption kinetics for hexanethiol is similar to that of propanethiol but taking place at higher rates, stressing the importance of the hydrocarbon chain length in the growth process. ISS-TOF measurements during thermal desorption show that most of the C, H, and S go away together, suggesting that the molecules adsorb and desorb from flat regions without S-C bond cleavage. Fitting the desorption maximum at 450 K with a first-order desorption curve gives a desorption energy of 1.43 eV. A small final S content that is correlated with the initial Ag(111) surface roughness is observed after desorption.

Letter↗

PubMed2006

Two-site adsorption model for the (square root 3 x square root 3)-R30 degrees dodecanethiolate lattice on Au(111) surfaces.

The surface structure of dodecanethiolate self-assembled monolayers (SAMs) on Au(111) surfaces, formed from the liquid phase, have been studied by grazing incidence X-ray diffraction (GIXRD), scanning tunneling microscopy (STM), and electrochemical techniques. STM images show that the surface structure consists of (square root 3 x square root 3)-R30 degrees domains with only a few domains of the c(4 x 2) lattice. The best fitting of GIXRD data for the (square root 3 x square root 3)-R30 degrees lattice is obtained with alkanethiolate adsorption at the top sites, although good fittings are also obtained for the fcc and hcp hollow sites. On the basis of this observation, STM data, electrochemical measurements, and previously reported data, we propose a two-site model that implies the formation of incoherent domains of alkanethiolate molecules at top and fcc hollow sites. This model largely improves the fitting of the GIXRD data with respect to those observed for single adsorption sites and, also, for the other possible two-site combinations. The presence of alkanethiolate molecules adsorbed at the less favorable top sites could result from the adsorption pathway that involves an initial physisorption step which, for steric reasons, takes place at on top sites. Once the molecules are chemisorbed, the presence of energy barriers for alkanethiolate surface diffusion, arising mostly from chain-chain interactions, "freezes" some of them at the on top sites, hindering their movement toward fcc hollow sites. By considering the length of the hydrocarbon chain and the adsorption time, the two-site model could be a tool to explain most of the controversial results on this matter reported in the literature.

Journal Article↗

PubMed2006

Modeling growth from the vapor and thermal annealing on micro- and nanopatterned substrates.

We propose a -dimensional mesoscopic model to describe the most relevant physical processes that take place while depositing and/or annealing micro- and nanopatterned solid substrates. The model assumes that a collimated incident beam impinges over the growing substrate; scattering effects in the vapor and reemission processes are introduced in a phenomenological way as an isotropic flow. Surface diffusion is included as the main relaxation process at the micro- or nanoscale. The stochastic model is built following population dynamics considerations; both stochastic simulations and the deterministic limit are analyzed. Numerical aspects regarding its implementation are also discussed. We study the shape-preserving growth mode, the coupling between shadowing effects and random fluctuations, and the spatial structure of noises using numerical simulations. We report important deviations from linear theories of surface diffusion when the interfaces are not compatible with the small slope approximation, including spontaneous formation of overhangs and nonexponential decay of pattern amplitudes. We discuss the dependence of stationary states with respect to the boundary conditions imposed on the system.

Journal Article↗

PubMed2006

Exploring three-dimensional nanosystems with Raman spectroscopy: methylene blue adsorbed on thiol and sulfur monolayers on gold.

Resonant Raman and surface-enhanced Raman scattering (SERS) spectroscopies, complemented with scanning tunnel microscopy and electrochemical techniques, have been used to obtain information about the amount and spatial distribution of methylene blue (MB) molecules immobilized on sulfur and four ultrathin molecular alkanethiolate films self-assembled on Au(111) and rough Au electrodes. The intensity of the Raman signals allow one to estimate the amount of immobilized MB at different organic films, whereas the decrease in the SERS intensity as a function of distance for the rough Au electrodes is used to locate the average position of the MB species with respect to the Au substrate. We found that significant amounts of cationic MB species are able to diffuse into methyl-terminated thiols, but they are stopped at the outer plane of the self-assembled monolayer (SAM) by negatively charged carboxylate groups. The relative shift of C-N stretching Raman modes indicates that the binding of MB to S is different from that found for MB on thiols. Most of the molecules immobilized on methyl- and carboxylate-terminated thiols are electrochemically inactive, suggesting that strong coupling between the Au electrode and the MB molecules is needed for charge transfer. Our results are consistent with a small population of electrochemically active MB species very close to the Au surface that reach this position driven by their lipophilic (hydrophobic) character through defects at SAMs.

Adsorption↗

PubMed2006

Immobilization of methylene blue on self-assembled iodine monolayers on gold.

The immobilization of methylene blue (MB) on iodine-covered Au(111) is studied by electrochemical techniques, scanning tunneling microscopy (STM), Auger Electron Spectroscopy (AES), and Raman spectroscopy. Results show that MB species are efficiently adsorbed on the square root of 3 x square root of 3 R30 degrees I lattice on Au(111). The electrochemical behavior of the adsorbed MB molecules is reversible, indicating a relatively fast electron transfer from the Au(111) surface to the immobilized MB species through the iodine layer. STM images with molecular resolution are consistent with adsorption of MB dimers on a square root of 3 x square root of 3 R30 degrees I lattice placed atop of the Au(111) substrate. Results are compared to those obtained for MB immobilized on Au(111) covered by S(n) (n = 3-8) surface structures.

Adsorption↗

PubMed2005

Electrochemical deposition onto self-assembled monolayers: new insights into micro- and nanofabrication.

Pattern transfer with high resolution is a frontier topic in the emerging field of nanotechnologies. Electrochemical molding is a possible route for nanopatterning metal, alloys and oxide surfaces with high resolution in a simple and inexpensive way. This method involves electrodeposition onto a conducting master covered by a self-assembled alkanethiolate monolayer (SAMs). This molecular film enables direct surface-relief pattern transfer from the conducting master to the inner face of the electrodeposit, and also allows an easy release of the electrodeposited film due their excellent anti-adherent properties. Replicas of the original conductive master can be also obtained by a simple two-step procedure. SAM quality and stability under electrodeposition conditions combined with the formation of smooth electrodeposits are crucial to obtain high-quality pattern transfer with sub-50 nm resolution.

Journal Article↗

PubMed2005

Electrochemical self-assembly of alkanethiolate molecules on Ni(111) and polycrystalline Ni surfaces.

In this work, the electrochemical formation of alkanethiolate self-assembled monolayers (SAMs) on Ni(111) and polycrystalline Ni surfaces from alkanethiol-containing aqueous 1 M NaOH solutions was studied by combining Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), electrochemical techniques, and density functional theory (DFT) calculations. Results show that alkanethiolates adsorb on Ni concurrent with NiO electroreduction. The resulting surface coverage depends on the applied potential and hydrocarbon chain length. Electrochemical and XPS data reveal that alkanethiolate electroadsorption at room temperature takes place without S-C bond scission, in contrast to previous results from gas-phase adsorption. A complete and dense monolayer, which is stable even at very high cathodic potentials (-1.5 V vs SCE), is formed for dodecanethiol. DFT calculations show that the greater stability against electrodesorption found for alkanethiolate SAMs on Ni, with respect to SAMs on Au, is somewhat related to the larger alkanethiolate adsorption energy but is mainly due to the larger barrier to interfacial electron transfer present in alkanethiolate-covered Ni. A direct consequence of this work is the possibility of using electrochemical self-assembly as a straightforward route to build stable SAMs of long-chained alkanethiolates on Ni surfaces at room temperature.

Journal Article↗

PubMed2005

Biomimetics with a self-assembled monolayer of catalytically active tethered isoalloxazine on Au.

A new biomimetic nanostructured electrocatalyst comprised of a self-assembled monolayer (SAM) of flavin covalently attached to Au by reaction of methylformylisoalloxazine with chemisorbed cysteamine is introduced. Examinations by Fourier transform infrared spectroscopy and scanning tunneling microscopy (STM) show that the flavin molecules are oriented perpendicular to the surface with a 2 nm separation between flavin molecules. As a result of the contrast observed in the STM profiles between areas only covered by unreacted cysteamine and those covered by flavin-cysteamine moieties, it can be seen that the flavin molecules rise 0.7 nm above the chemisorbed cysteamines. The SAM flavin electrocatalyst undergoes fast electron transfer with the underlying Au and shows activity toward the oxidation of enzymatically active beta-NADH at pH 7 and very low potential (-0.2 V vs Ag/AgCl), a requirement for use in an enzymatic biofuel cell, and a 100-fold increase in activity with respect to the collisional reaction in solution.

Biomimetics↗

PubMed2005

Electrochemical self-assembly of melanin films on gold.

An electrochemical method for self-assembling melanin films on the Au(111) surface from melanin aggregates in alkaline media is reported. Electrochemical data combined with scanning tunneling microscopy (STM), atomic force microscopy, and Auger electron spectoscopy show that the amount and structure of the deposited melanin film depend on the potential (E) applied to the electrochemical interface and deposition time. Film formation takes place at a noticeable rate at E = -1.0 V (vs SCE). High-resolution STM images at the early stages of growth show small particles, 5-8 nm in size and 0.3-0.4 nm in height, forming ordered arrays that follow closely the Au(111) topography. The size of the melanin particles increases as the film thickness increases, reaching 150 nm for deposits grown for 16 h. The deposited films are electrochemically active, showing well-defined redox couples preceding the hydrogen evolution reaction.

Biofilms↗

PubMed2005

Molding and replication of ceramic surfaces with nanoscale resolution.

The design of reproducible and more efficient nanofabrication routes has become a very active research field in recent years. In particular, the development of new methods for micro- and nanopatterning materials surfaces has attracted the attention of many researchers in industry and academia as a consequence of the growing relevance of patterned surfaces in many technological fields, ranging from optoelectronics to biotechnology. In this work we explore, discuss, and demonstrate the possibility of extending the well-known molding and replication strategy for patterning ceramic materials with nanoscale resolution. To achieve this goal we have combined physical deposition methods, molecule-thick anti-sticking coatings, and nanostructured substrates as master surfaces. This new perspective on an "old technology", as molding is, provides an interesting alternative for high-resolution, direct surface-relief patterning of materials that currently requires expensive and time-consuming lithographic approaches.

Biocompatible Materials↗

PubMed2004

Probing universality classes in solid-on-solid deposition.

We consider several stochastic processes corresponding to the same physical solid-on-solid deposition problem. Simplified models presenting the same (conditional) mean and variance for each process are also introduced as well as generalizations in terms of the deposition of blobs and probabilistic deposition rules. We compare the evolution of the roughness as a function of time for a three-parameter family that includes as limit cases the Family model and the Edwards-Wilkinson equation, showing that in all cases the derived models with the same mean and variance are indistinguishable from the originating models in terms of the evolution of the roughness. Finally, we show that although all the models studied belong to the same universality class, some relevant features such as the final surface roughness are reproduced only for models within a restricted class determined by sharing the same (conditional) mean and variance.

Journal Article↗

PubMed2003

Dynamics of solid growth under a gravitational field: influence of the formation of a diffusive layer.

We discuss the gravitational sedimentation of particles in terms of a stochastic model considering, in view of experimental evidence, that the aggregation to the growing surface (deposit) is mediated by the formation of a layer of suspended particles subject to gravitational forces, thermal agitation, as well as aggregation (contact) forces. The aggregation of such partially buoyant particles is ruled by the rates of occurrence of the different stochastic events: incorporation to the layer of suspended particles, sedimentation, and gravitationally biased diffusion. The model introduces bridges across different standard solid on solid deposition models which can be considered as limit cases of the present one. Analytical and numerical results show that for finite (realistic) deposits there are different regimes of aggregation including situations in which the deposit is grown completely during the transient time of the system.

Journal Article↗