Abstract:

Many systems of interest to researchers in Two-Dimensional Infrared Spectroscopy (2D IR), particularly in the study of polymers have been limited by scattering removal methods which significantly increase the data collection time, reducing the number of averages a researcher can acquire in a period of time, and limiting the polarization schemes available. This dissertation details a method for removing scattering which considers the detector nonlinearity and the artifacts caused by this, enabling researchers to remove scattering using fewer shots and utilize many different polarization schemes. This method of scattering removal was then applied to dibenzocycloocta-1,5-dien (DBCOD) to determine the conformation at different temperatures and moisture levels. It has been hypothesized that DBCOD monomers go from predominantly twist boat to predominantly chair conformation with rising temperatures. This was proposed to explain the macroscopic contraction observed when heating DBCOD based polymer films. This dissertation supports the conclusion that temperature increases chair conformation but does not find predominantly chair conformation in dry conditions, even at high temperatures. Additionally, this dissertation evaluates the effects of water on the population of chair and twist boat conformation and finds evidence that water increases the chair conformation. Finally, the encapsulation of Nile red in biodegradable, amphiphilic block copolymer polyethylene glycol-block-polycaprolactone (PEG45-b-PCL30) was confirmed and the dynamics were characterized using nonlinear least squares fitting of the data to Redfield equations which track the population and coherence transfer.