The controlled patterning of polymeric surfaces at the micro- and nanoscale offers potential in the technological development of small-scale devices, particularly within the fields of photovoltaics, micro-optics and lab- and organ-on-chip, where the topological arrangement of the surface can influence a system's power generation, optical properties or biological function - such as, in the latter case, biomimicking surfaces or topological control of cellular differentiation. One of the most promising approaches in reducing manufacturing costs and complexity is by exploitation of the self-assembling properties of colloidal particles. Self-assembly techniques can be used to produce colloidal crystals onto surfaces, which can act as replicative masks, as has previously been demonstrated with colloidal lithography, or templates in mold-replication methods with resolutions dependent on particle size. Within this context, a particular emerging interest is focused on the use of self-assembled colloidal crystal surfaces in polymer replication methods such as soft lithography, hot and soft embossing and nano-imprint lithography, offering low-cost and high-resolution alternatives to conventional lithographic techniques. However, there are still challenges to overcome for this surface patterning approach to reach a manufacturing reliability and process robustness comparable to competitive technologies already available in the market, as self-assembly processes are not always 100% effective in organizing colloids within a structural pattern onto the surface. Defects often occur during template fabrication. Furthermore, issues often arise mainly at the interface between colloidal crystals and other surfaces and substrates. Particularly when utilized in high-temperature pattern replication processes, poor adhesion of colloidal particles onto the substrate results in degradation of the patterning template. These effects can render difficulties in creating stable structures with little defect that are well controlled such that a large variety of shapes can be reproduced reliably. This review presents an overview of available self-assembly methods for the creation of colloidal crystals, organized by the type of forces governing the self-assembly process: fluidic, physical, external fields, and chemical. The main focus lies on the use of spherical particles, which are favorable due to their high commercial availability and ease of synthesis. However, also shape-anisotropic particle self-assembly will be introduced, since it has recently been gaining research momentum, offering a greater flexibility in terms of patterning. Finally, an overview is provided of recent research on the fabrication of polymer nano- and microstructures by making use of colloidal self-assembled templates.

A surface modification of interdigitated gold microelectrodes (IDEs) with a doped polypyrrole (PPy) film for detection of dopamine released from populations of differentiated PC12 cells is presented. A thin PPy layer was potentiostatically electropolymerized from an aqueous pyrrole solution onto electrode surfaces. The conducting polymer film was doped during electropolymerization by introducing counter-ions in the monomer solution. Several counter-ions were tested and the resulting electrode modifications were characterized electrochemically to find the optimal dopant that increases sensitivity in dopamine detection. Overoxidation of the PPy films was shown to contribute to a significant enhancement in sensitivity to dopamine. The changes caused by overoxidation in the electrochemical behavior and electrode morphology were investigated using cyclic voltammetry and SEM as well as AFM, respectively. The optimal dopant for dopamine detection was found to be polystyrene sulfonate anion (PSS⁻). Rat pheochromocytoma (PC12) cells, a suitable model to study exocytotic dopamine release, were differentiated on IDEs functionalized with an overoxidized PSS⁻-doped PPy film. The modified electrodes were used to amperometrically detect dopamine released by populations of cells upon triggering cellular exocytosis with an elevated K⁺ concentration. A comparison between the generated current on bare gold electrodes and gold electrodes modified with overoxidized doped PPy illustrates the clear advantage of the modification, yielding 2.6-fold signal amplification. The results also illustrate how to use cell population based dopamine exocytosis measurements to obtain biologically significant information that can be relevant in, for instance, the study of neural stem cell differentiation into dopaminergic neurons.

Protein nanofibrils offer advantages over other nanostructures due to the ease in their self-assembly and the versatility of surface chemistry available. Yet, an efficient and general methodology for their post-assembly functionalization remains a significant challenge. We introduce a generic approach, based on biotinylation and thiolation, for the multi-functionalization of protein nanofibrils self-assembled from whey proteins. Biochemical characterization shows the effects of the functionalization onto the nanofibrils' surface, giving insights into the changes in surface chemistry of the nanostructures. We show how these methods can be used to decorate whey protein nanofibrils with several components such as fluorescent quantum dots, enzymes, and metal nanoparticles. A multi-functionalization approach is used, as a proof of principle, for the development of a glucose biosensor platform, where the protein nanofibrils act as nanoscaffolds for glucose oxidase. Biotinylation is used for enzyme attachment and thiolation for nanoscaffold anchoring onto a gold electrode surface. Characterization via cyclic voltammetry shows an increase in glucose-oxidase mediated current response due to thiol–metal interactions with the gold electrode. The presented approach for protein nanofibril multi-functionalization is novel and has the potential of being applied to other protein nanostructures with similar surface chemistry.

In this paper we demonstrate the fabrication and electrochemical characterization of a microchip with 12 identical but individually addressable electrochemical measuring sites, each consisting of a set of interdigitated electrodes acting as a working electrode as well as two circular electrodes functioning as a counter and reference electrode in close proximity. The electrodes are made of gold on a silicon oxide substrate and are passivated by a silicon nitride membrane. A method for avoiding the creation of high edges at the electrodes (known as lift-off ears) is presented. The microchip design is highly symmetric to accommodate easy electronic integration and provides space for microfluidic inlets and outlets for integrated custom-made microfluidic systems on top.

In this paper we present a series of experiments showing that vertical self-assembled diphenylalanine peptide nanowires (PNWs) are a suitable candidate material for cellular biosensing. We grew HeLa and PC12 cells onto PNW modified gold surfaces and observed no hindrance of cell growth caused by the peptide nanostructures; furthermore we studied the properties of PNWs by investigating their influence on the electrochemical behavior of gold electrodes. The PNWs were functionalized with polypyrrole (PPy) by chemical polymerization, therefore creating conducting peptide/polymer nanowire structures vertically attached to a metal electrode. The electroactivity of such structures was characterized by cyclic voltammetry. The PNW/PPy modified electrodes were finally used as amperometric dopamine sensors, yielding a detection limit of 3,1 microM.