The final step in the supramolecular buildup of eumelanin particles is investigated regarding the involved species and mechanism. Time-resolved in situ light scattering and scanning electron microscopy reveal an aggregation of particles with a narrow size distribution around 40 nm, previously only observed as substructures. These form larger particles with again very uniform size and diameters around 200 nm. Aggregation of each single particle takes only a few minutes to complete, whereas the entire process goes on for at least 3 h, partly due to the kinetics of the precursors. The individual particles also undergo an additional consolidation step toward their final form, which takes up to 24 h. Atomic force microscopy shows that the size before consolidation is around twice the size of the final particles, due to free space between the substructures. Light scattering also reveals that the aggregation is random with respect to where the particles attach, as the shape of aggregates changes from sphere to coil, before it returns to a spherical shape at the end. Application of enzyme mediated autodeposition finally shows the potential to stop the supramolecular buildup at each level, and therefore enables isolation of the respective eumelanin particles at will. This may enable the full potential for melanin materials in nanotechnology deriving from its unique (for biological polymers) properties like paramagnetism, electrical conductivity, and many more.
Research on the supramolecular buildup of eumelanin has gained high momentum in the last years. Several new aspects regarding the involved structures and mechanisms have been established, which has led to a better understanding of the entire process. This review intends to provide a clearly laid-out summary of previous and new findings regarding structures, mechanisms, and controllability. With respect to materials applications, the aspect of controllability is of supreme importance. A focus of this review is therefore set on a novel method with high potential for specific synthesis of various, isolated particle morphologies. Finally, open questions and possibilities for their elucidation are discussed.
A method for in situ formation and controlled deposition of eumelanin nanoparticles is presented. The particles are built up by enzymatic reaction of l-DOPA with tyrosinase. The enzyme is tethered onto the support surface to get site-specific deposition of eumelanin. Due to the immediate deposition, the particles are monodisperse, with diameters of about 30-60 nm. Up to now, eumelanin particles have only been observed with sizes of about 200 nm. Deposition of those particles is site-specific on the areas where enzyme is present and results in different kinds of patterns on the support surface, including versatile monolayer structures.
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