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.
","abstract_html":"<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 Ni<sup>0</sup>-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 CH<sub>2</sub>Cl<sub>2</sub>. 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>","abstract_has_math":false,"creators":["Lema, Manuel A"],"institution":null,"degree_name":"Master of Science (M.S.)","degree_level":"Thesis","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Barbara Zajc"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2022,"date_issued":"2022-01-01T08:00:00Z","date_published":"2022-01-01T08:00:00Z","updated_at":"2026-07-24T01:57:53Z","subjects":["Mucin","Mucus","Snail","Galactose","Threonine","Polymer","Organic Chemistry","Polymer Chemistry"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://academicworks.cuny.edu/cc_etds_theses/1001","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Barbara Zajc"]},{"key":"dc:creator","label":"Author","values":["Lema, Manuel A"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.available","label":"Dc Date Available","values":["2024-05-04T07:00:00Z"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Thesis"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Master of Science (M.S.)"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Mucin","Mucus","Snail","Galactose","Threonine","Polymer","Organic Chemistry","Polymer Chemistry"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://academicworks.cuny.edu/cc_etds_theses/1001"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["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.
"]},{"key":"dc:title","label":"Title","values":["Poly(β-Gal-Thr): A New Scalable Synthetic Mucin"]}]}],"canonical_facts":{"dc:contributor":["Barbara Zajc"],"dc:creator":["Lema, Manuel A"],"dc:date.available":["2024-05-04T07:00:00Z"],"dc:description.abstract":["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.
"],"dc:identifier":["https://academicworks.cuny.edu/cc_etds_theses/1001"],"dc:subject":["Mucin","Mucus","Snail","Galactose","Threonine","Polymer","Organic Chemistry","Polymer Chemistry"],"dc:title":["Poly(β-Gal-Thr): A New Scalable Synthetic Mucin"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Thesis"],"thesis:degree_name":["Master of Science (M.S.)"]},"updated_at":"2026-07-24T01:57:53Z"}