Date of Award

Spring 2020

Project Type


Program or Major


Degree Name

Doctor of Philosophy

First Advisor

Samuel Pazicni

Second Advisor

Roy P Planalp

Third Advisor

Christopher F Bauer


The branch of biomimetic chemistry aims to imitate natural reactions and enzymatic processes in order to advance many other areas of chemistry, including inorganic and organic catalysis as well as materials science. To study the mechanisms of enzyme activity and the effect of secondary coordination sphere interactions, the synthesis and characterization of two artificial metallo-enzymes were pursued.

In order to further understand the mechanism of [FeFe]-hydrogenase and the effect of secondary coordination sphere interactions within the protein binding pocket, the synthesis of an optimized biotin-avidin [FeFe] artificial enzyme was pursued. This dissertation describes the synthesis and characterization of the small molecule components explored for the insertion of an azadithiolato bridged [FeFe] cluster into avidin or streptavidin in order to generate a novel biotin-avidin [FeFe] hydrogenase. While further research is required in order to obtain the desired aza-bridged [FeFe] cluster compatible with insertion into avidin, the insight obtained through the attempted synthesis herein may aid others in their synthesis of [FeFe]-hydrogenase model complexes.

In order to study heme enzymes, a suite of zinc porphyrin-cored random coil polymers and polymeric nanoparticles with varying degrees of potential hydrogen bonding character and steric bulk were synthesized to study secondary coordination sphere interactions. Cyanide binding studies intended to probe for hydrogen bonding environments generated by the polymer scaffold resulted in the catalytic reaction of cyanide with the solvent N,N-dimethylformamide. The reaction of cyanide with N,N-dimethylformamide in the presence of the biomimetic polymers was monitored via UV-Vis spectroscopy. The spectroscopic data lead to the determination that the collapsed topology of the polymeric nanoparticles led to higher catalytic activity than that of the random coil polymers with the fastest reactions rates occurring with polymeric nanoparticles with a greater number of potential hydrogen bond donors and larger steric bulk.