Adsorption of 2-mercaptobenzimidazole on a Au(1 1 1) electrode

The description of the monolayer formed at Au(1 1 1) by 2-mercaptobenzimidazole (MBI) under potential control has been based on electrochemical data (charge measurements) and spectroscopic information from the subtractively normalized interfacial Fourier transform infrared spectroscopy method (SNIFTIRS). From the quantitative analysis of the SNIFTIR spectra, a surface coverage Γ/Γmax was extracted for each sample potential. The evolution of the coverage with potential was in full agreement with the charge density curve. The shift of the pzc in the presence of MBI indicates that the adsorbed molecules have a nonzero component of the permanent dipole moment in the direction perpendicular to the electrode surface. Thanks to the high quality of the spectra, it was possible to determine the orientation of MBI molecules at the surface in the monolayer and submonolayer range. The angle between the C2-axis of the molecule and the direction normal to the surface is close to 64 ± 4° and its small change (<15°) with potential indicates that the orientation of the molecules is chiefly controlled by the chemical interaction between the sulphur atom and the gold surface. © 2005 Elsevier Ltd. All rights reserved.

On the adsorption of hexaammineruthenium (III) at anionic self-assembled monolayers

The binding of the electroactive hexaammineruthenium (III) complex ions to anionic self-assembled monolayers (SAMs) has been investigated by means of chronocoulometry and ac voltammetry. From chronocoulometric data recorded in 10-2 M LiClO4 containing different [Ru(NH3)6]3+ concentrations, we have established the adsorption isotherm of [Ru(NH3)6]3+ on a compact monolayer of 2-mercaptobenzimidazole-5-sulfonate (MBIS) self-assembled on Au(1 1 1). The data were satisfactorily fitted to the linearized Langmuir adsorption isotherm and a binding constant of 4.0 (±0.4) × 106 M-1 has been determined. The electrostatic binding of [Ru(NH3)6]3+ to a dilute PNA-DNA monolayer formed after hybridization on a PNA-modified gold electrode by self-assembly from a mixed solution of mercaptobutan-1-ol and PNA oligonucleotides has been studied by ac voltammetry. The admittance of the PNA-modified electrode after hybridization with complementary DNA was measured in 0.01 M Tris-HCl buffer containing different [Ru(NH3)6]3+ concentrations. Based on these data, a binding constant of [Ru(NH3)6]3+ to the surface-confined PNA-DNA duplex was derived from the Langmuir isotherm and amounts to 2.9 (±0.3) × 105 M-1. As the interactions between [Ru(NH3)6]3+ and the immobilized PNA-DNA hybrids on the gold surface are essentially electrostatic, the adsorption of the highly charged cationic redox complex at low concentrations to the negatively charged PNA-DNA modified surface is in large competition with other monovalent cations present in the electrolyte at higher concentrations. The influence of competing sodium cations was thus studied by adding different NaCl concentrations in the 0.01 M Tris-HCl electrolyte. © 2008 Elsevier Ltd. All rights reserved.

Surface area, porosity and water adsorption properties of fine volcanic ash particles

Our understanding on how ash particles in volcanic plumes react with coexisting gases and aerosols is still rudimentary, despite the importance of these reactions in influencing the chemistry and dynamics of a plume. In this study, six samples of fine ash (<100 μm) from different volcanoes were measured for their specific surface area, as, porosity and water adsorption properties with the aim to provide insights into the capacity of silicate ash particles to react with gases, including water vapour. To do so, we performed high-resolution nitrogen and water vapour adsorption/desorption experiments at 77 K and 303 K, respectively. The nitrogen data indicated as values in the range 1.1-2.1 m2/g, except in one case where as of 10 m2/g was measured. This high value is attributed to incorporation of hydrothermal phases, such as clay minerals, in the ash surface composition. The data also revealed that the ash samples are essentially non-porous, or have a porosity dominated by macropores with widths >500 Å All the specimens had similar pore size distributions, with a small peak centered around 50 Å These findings suggest that fine ash particles have relatively undifferentiated surface textures, irrespective of the chemical composition and eruption type. Adsorption isotherms for water vapour revealed that the capacity of the ash samples for water adsorption is systematically larger than predicted from the nitrogen adsorption as values. Enhanced reactivity of the ash surface towards water may result from (i) hydration of bulk ash constituents; (ii) hydration of surface compounds; and/or (iii) hydroxylation of the surface of the ash. The later mechanism may lead to irreversible retention of water. Based on these experiments, we predict that volcanic ash is covered by a complete monolayer of water under ambient atmospheric conditions. In addition, capillary condensation within ash pores should allow for deposition of condensed water on to ash particles before water reaches saturation in the plume. The total mass of water vapour retained by 1 g of fine ash at 0.95 relative water vapour pressure is calculated to be ∼10-2 g. Some volcanic implications of this study are discussed. © Springer-Verlag 2004.