Poly(β-Gal-Thr): A New Scalable Synthetic Mucin

<p>A method for the preparation of glycosylated polypeptides via the nucleophilic ring-opening polymerization of a glycosylated <em>N</em>-carboxyanhydride (NCA) monomer is reported. The synthesis of 2,3,4,6-tetraacetyl-<em>β</em>-galactose-threonine <em>N</em>-carboxyanhydride (<em>β</em>-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 (<em>Ð)</em>, 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.</p>

Name thesis:degree_name

Master of Science (M.S.)

Level thesis:degree_level

Thesis

Discipline thesis:degree_discipline

Chemistry

Year dc:date.available

2022

Author dc:creator

• Lema, Manuel A

Contributors dc:contributor

• Barbara Zajc

• Mucin
• Mucus
• Snail
• Galactose
• Threonine
• Polymer
• Organic Chemistry
• Polymer Chemistry

Repository record dc:identifier

https://academicworks.cuny.edu/cc_etds_theses/1001

OAI identifier oai:identifier

oai:academicworks.cuny.edu:cc_etds_theses-2041