The aggregation of Au nanoparticles in solution is induced and influenced by cationic and oligocationic species. This solution-state aggregation bears similarities to multilayer formation on surfaces but is more facile because of the nanoparticles' intrinsic instability in solution. Aggregation is followed by transmission electron microscopy (TEM) and the appearance of features at lambda = 600-900 nm in the absorbance spectrum. It is found that these features are a function of factors such as the aggregant size, charge, and concentration, and the method of mixing the components, and they can be related to aggregate morphology. It seems that there are two mechanisms that can act to cause aggregation. Multiply charged aggregants can bind nanoparticles together into dense aggregates, displaying a defined absorbance at ca. lambda = 700 nm, whereas singly charged aggregants cause a slower aggregation into string-like aggregates with a less defined absorbance. Whereas multiply charged aggregants can cross-link the layers in a multilayer structure on a surface, singly charged aggregants cannot.
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