Experimental investigations were made into the effects of monomer structure and functionality on free-radical polymerization kinetics. A more comprehensive understanding of how structural characteristics, monomer traits, and polymerization conditions influence the polymerization mechanisms and network evolution was desired. Variations in the nature of the monomers' secondary functionality and the terminal substitution were the primary variables examined. The three factors hypothesized as important to the advantageous polymerization characteristics observed are hydrogen bonding, hydrogen abstraction, and the electronic characteristics of the monomer. The experimental evaluations presented clearly demonstrate that each of these mechanisms contributes to the reactivity of these monomers and the networks that they form. The combination of these factors leads to crosslinked network formation and enhanced polymerization kinetics, i.e., monovinyl monomers with reactivities that rival those of commonly used divinyl monomers.

Plasma‐enhanced chemical vapor patterned surfaces are used for site‐ specific attachment of biomolecules and semiconductor quantum dots (QDs; see figure). The fabrication of surfaces with multiple functional building blocks can be used in a single step to create complex multifunctional patterned substrates incorporating self‐assembled monolayers (SAMs) and thiol‐functionalized quantum dots for a variety of applications.