Adsorption Behavior of 5-Fluorouracil on Au(111): An In Situ STM Study

The biological effects of chemical substitution of DNA bases triggered several investigations of their physicochemical properties This paper studies the adsorption behavior of a halogenated uracil, 5-fluorouracil (5FU). at the electrochemical interface of Au(111) and sulfuric acid solution. Upon modulation of the electric field across the interface, four distinct phases could be inferred by means of cyclic voltammetry (CV) At negative potentials relative to the SCE electrode, limited by the threshold of hydrogen evolution, no molecular species could be detected by scanning tunneling microscopy (STM) at the reconstructed Au(111)-(23 x root 3) surface, indicating that any physisorbed molecules are randomly distributed Incursion into more positive potentials increases the surface population but doer not form any two-dimensional (2D) physisorbed ordered structure Instead, we observed metastable structures that are only detectable. on surfaces with high defect density At sufficiently high positive potentials. limited by gold oxidation, the molecules are chemisorbed in a (3 x 2 root 3) ordered structure. with the aromatic ring perpendicular to the surface We report the densest chemisorbed monolayer for pyrimidine-derivative molecules (area per molecule 0 14 +/- 0 04 nm(2)). A comparison of the adsorption behavior of uracil derivatives has been made based on recent results of chemical substitution and solvent effects. We propose that pi-stacking is enhanced when halogens are incorporated in the uracil structure, in a similar fashion to what is observed in then crystal structure

Using Polycarbonate Membranes as Templates for the Preparation of Au Nanostructures for Surface-Enhanced Raman Scattering

Polycarbonate membranes (PCM) of various pores sizes (400, 200, 100 and 50 nm) were used as templates for gold deposition. The electrodeposition from gold ions resulted in the formation of gold nanotubes when large pores size PCMs (400 and 200 nm) were used. On the other hand, gold nanowires were predominant for the PCMs with smaller pores size (100 and 50 nm). Surface-enhanced Raman scattering (SERS) from the probe molecule 4-mercaptopyridine (4-MPy) was obtained from all these nanostructures. The SERS efficiency of the substrates produced using the PC M templates were compared to two commonly used SERS platforms: a roughened gold electrode and gold nanostructures electrodeposited through organized polystyrene spheres (PSS). The SERS signal of the probe molecule increased as the pore diameter of the PCM template decreased. Moreover, the SERS efficiency from the nanostructures produced using 50 nm PCM templates was four and two times better than the signal from the roughened gold electrode and the PSS template, respectively. The SERS substrates prepared using PCM templates were more homogenous over a larger area (ca. 1 cm(2)), presented better spatial and sample to sample reproducibility than the other substrates. These results show that SERS substrates prepared using PCM templates are promising for the fabrication of planar SERS platforms for analytical/bioanalytical applications.

Deposition of selenium thin layers on gold surfaces from sulphuric acid media: Studies using electrochemical quartz crystal microbalance, cyclic voltammetry and AFM

In this paper we report here new considerations about the relationship between the mass and charge variations (m/z relationship) in underpotential deposition (UPD), bulk deposition and also in the H(2)Se formation reaction. Nanogravimetric experiments were able to show the adsorption of H(2)SeO(3) on the AuO surface prior to the voltammetric sweep and that, after the AuO reduction, 0.40 monolayer of H(2)SeO(3) remains adsorbed on the newly reduced Au surface, which was enough to gives rise to the UPD layer. The UPD results indicate that the maximum coverage with Se(ads) on polycrystalline gold surface corresponds to approximately 0.40 monolayer, in good agreement with charge density results. The cyclic voltammetry experiments demonstrated that the amount of bulk Se obtained during the potential scan to approximately 2 Se monolayers, which was further confirmed by electrochemical quartz crystal microbalance (EQCM) measurements that pointed out a mass variation corresponding of 3 monolayers of Se. In addition, the Se thin films were obtained by chronoamperometric experiments, where the Au electrode was polarized at +0.10V during different times in 1.0 M H(2)SO(4) + 1.0 mM SeO(2). The topologic aspects of the electrodeposits were observed in Atomic Force Microscope (AFM) measurements. Finally, in highly negative potential polarizations, the H(2)Se formation was analyzed by voltammetric and nanogravimetric measurements. These finding brings a new light on the selenium electrodeposition and point up to a proposed electrochemical model for molecule controlled surface engineering. (c) 2009 Elsevier Ltd. All rights reserved.

The interaction between atoms of Au and Cu with clean Si(111) surface: A study combining synchrotron radiation grazing incidence X-ray fluorescence analysis and theoretical calculations

In order to evaluate the interactions between Au/Cu atoms and clean Si(l 11) surface, we used synchrotron radiation grazing incidence X-ray fluorescence analysis and theoretical calculations. Optimized geometries and energies on different adsorption sites indicate that the binding energies at different adsorption sites are high, suggesting a strong interaction between metal atom and silicon surface. The Au atom showed higher interaction than Cu atom. The theoretical and experimental data showed good agreement. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.