In situ surface plasmon resonance (SPR) spectroscopy methods are used to investigate the process by which thin films form at solid/solutions interfaces. Representative kinetics data are presented for the adsorption of two different types of molecular adsorbates onto gold substrates. The first system involves adsorption of alginic acid, an acidic polysaccharide. The second system involves the adsorption of single-stranded DNA oligomers. Quantitative two-color SPR kinetics data are of sufficiently high quality that distinguishing between various kinetics models is now possible. Commonly used Langmuir adsorption models cannot adequately describe some of the adsorption kinetics data. However, these data are very well described by a model developed to include diffusion at the interface as well as adsorption/description. This more general model is found to work very well for a variety of chemically distinct adsorbate/substrate systems. Analysis of high quality in- situ SPR data can identify distinct differences in kinetics and many be useful for distinguishing between different types of adsorbate/surface interactions. This capability may prove very useful for gaining insight into mechanistic differences in the process by which molecular films at solid/liquid interfaces.
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