Dissertations and Theses

Date of Award


Document Type




First Advisor

Barbara Zajc


Mucin, Mucus, Snail, Galactose, Threonine, Polymer


A method for the preparation of glycosylated polypeptides via the nucleophilic ring-opening polymerization of a glycosylated N-carboxyanhydride (NCA) monomer is reported. The synthesis of 2,3,4,6-tetraacetyl-β-galactose-threonine N-carboxyanhydride (β-AcO-Gal-Thr-NCA) monomer in 5 steps with an 8 % overall yield is described, and the single-crystal X-ray structure is provided. The effect of a series of Ni0-based organometallic initiators, nucleophilic amine initiators, co-catalysts, and solvents on the polymerization were explored. The kinetics of the three most promising conditions were studied in greater detail. The conditions that provided the highest yield, low polydispersity (Ð), and excellent control over degree of polymerization ( ), while being amenable to gram-scale reactions, involved the nucleophilic initiator lithium hexamethyldisilazide (LiHMDS) and the cocatalyst 1,3-bis(2-hydroxyhexafluoroisopropyl) benzene (HFAB) in the nonpolar solvent CH2Cl2. A detailed analysis of this polymerization revealed that two propagation reactions proceed simultaneously, although at substantially different rates. These optimized polymerization conditions provide a route towards the synthesis of polymers that mimic the structures and properties of the highly glycosylated PTS domains of secreted mucin proteins.

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