Advances in applications from electronic device manufacturing to the controlled display of complex biomolecules require interfaces with precisely constructed chemical environments at micrometer and nanometer scales. The challenges of precisely structuring interfaces include not only positioning functional groups on the surface, but also controlling their orientation and clustering. Microcontact printing (μCP) enables geometrically patterned assembly over microscopic (or large nanoscopic) areas. However, traditional μCP, such as alkanethiols on gold, creates interfacial lattices with molecular footprints (~0.25 nm<sup>2</sup>) smaller than many biomolecules. Striped phase monolayers, in which noncovalently adsorbed alkyl chains extend across the substrate, have larger, more complex lattices (<i>i.e.</i> nm-wide stripes of headgroups with 0.5 or 1-nm lateral periodicity along the row, separated by wider (~5 nm) stripes of exposed alkyl chains). These anisotropic interfacial patterns provide a potential route to controlled clustering of complex functional groups. Here, we demonstrate that, with appropriate modifications, microcontact printing can be used to generate well-defined microscopic areas of noncovalently adsorbed striped phases of both single-chain amphiphiles (fatty acids) and dual-chain amphiphiles (phospholipids). This approach generates hierarchical molecular-scale and microscale interfacial clustering of functional ligands, prototyping a strategy of potential relevance for controlled clustering of complex functional groups.

Noncovalent microcontact printing for hierarchically patterned striped phases of polymerized lipids

2019 Fall National Meeting

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