The study of supramolecular structures for the purpose of creating efficient catalytic systems has been ongoing for the past several decades.  Studies of m-phenylene ethynylene (mPE) foldamers have shown that the helical binding cavity formed by the folded structure is capable of differentiating reactive guest substrates based on their size and shape, demonstrating a behavior we have termed "reactive sieving".  We have employed the methylation of a 4-dimethylaminopyridine (DMAP) moiety incorporated into the foldamer backbone to observe the effects of foldamer-based molecular recognition on reactivity.  To explore this concept in greater detail we have varied the position of the DMAP to determine its positional effect on reactivity, and performed molecular dynamics simulations to obtain qualitative information about the structure of the host-guest complex.  To examine the contribution of foldamer backbone flexibility to this phenomenon, a reductive amination based crosslinking strategy designed to restrict conformational freedom of the structure is demonstrated.