The synthesis of polymers (particularly conducting polymers) in confined areas and volumes
is of great interest as a strategy in microstructure and nanostructure fabrication. Our interest
is oriented toward the formation of new morphologies created by preferential surface
templating. In this report, we describe the polymerization of pyrrole (py) in the presence of
diacetylenic phospholipid tubules. These tubules, much studied by Schnur, Yager, and co-workers, are ∼500 nm wide and several micrometers long. Ppy growth is templated
specifically on the edges/seams of the tubule and not on its walls. An unusual long strand
morphology (10−100 nm wide and micrometers long) results. Attempts to alter the balance
between template (i.e., edged-localized) polymerization and solution polymerization reveals
that the propensity for template polymerization is overwhelmingly large. The properties of
the Ppy thus obtained, and possible templating mechanisms are discussed.
Arrays of polypyrrole (Ppy) dots (80−180 nm diameter) have been prepared in a highly parallel fashion. This process is achieved by templating
Ppy growth on a 2D surface micelle array, initially formed by the Langmuir−Blodgett (LB) technique. Ppy growth on self-assembled (SA)-based surface micelles produces more complex structures, due to simultaneous reorganization of the SA micelles. These results demonstrate
that template growth of conducting polymers can be used to fabricate configurations that are otherwise inaccessible.
The kinetics of alkylthiol-capped gold nanoparticle (RS/Au-NP) adsorption to alkylthiol/Au self-assembled monolayers (RS/Au-SAMs) has been studied using SPR (surface plasmon resonance) spectroscopy. Variation of the alkylthiol chain terminus (CH3, COOH) and solvent (H2O, hexane) provides insight into the relative importance of solvation energies (in the context of surface energies) and RS/Au-NP structure on adsorption kinetics. The kinetics, fitted to the Langmuir kinetic model, yield adsorption and desorption rate constants. DeltaG(ads) derived from kinetic data are compared to calculated values of work of adhesion (W(adh)), derived from the corresponding surface energies. The absence of a deltaG(ads) - W(adh) correlation arises because the measured kinetics are not reporting the approach to equilibrium and/or because there are factors (i.e., local chain packing defects, surface hydration differences, or particle-particle interactions) not accounted for in calculated W(adh) values.
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