Reactive Sieving With M-Phenylene Ethynylene Foldamers: Effects of Structural Modification on Reactivity

In an attempt to further understand the nature of the host-guest interaction between mPE foldamers and the methylsulfonate esters used to study reactive sieving, a set of parameters for both the mPE foldamer and the methylsulfonate guests were developed for CHARMM-based molecular dynamics simulations. A total of 14 simulations were performed (500 ps each) and the dihedral angles of the guest alkyl chains were monitored. It was found that many of the dihedral angles could adopt and maintain a gauche conformation during the course of the simulation. Furthermore, a correlation between a number of gauche configurations in the alkyl chain and the relative rate of methylation was observed. Although the sample size and simulation time were too small to make any strong conclusions, these parameters provide a starting point for more sophisticated and lengthy simulations.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2015

Author dc:creator

• Smaldone, Ronald A.

Contributors dc:contributor

• Moore, Jeffrey S.

• Chemistry, Organic

Language dc:language

eng

Identifier

(MiAaPQ)AAI3337926

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/87891