A Mechanistic Study of alpha-(Amino acid)-N-carboxyanhydride Polymerization: Comparing Initiation and Termination Events in High-Vacuum and Traditional Polymerization Techniques
Φόρτωση...
Ημερομηνία
Συγγραφείς
Pickel, D. L.
Politakos, N.
Avgeropoulos, A.
Messman, J. M.
Τίτλος Εφημερίδας
Περιοδικό ISSN
Τίτλος τόμου
Εκδότης
American Chemical Society
Περίληψη
Τύπος
Είδος δημοσίευσης σε συνέδριο
Είδος περιοδικού
peer reviewed
Είδος εκπαιδευτικού υλικού
Όνομα συνεδρίου
Όνομα περιοδικού
Macromolecules
Όνομα βιβλίου
Σειρά βιβλίου
Έκδοση βιβλίου
Συμπληρωματικός/δευτερεύων τίτλος
Περιγραφή
High-vacuum polymerization of alpha-(amino acid)-N-carboxyanhydrides (NCAs) affords polymers with controlled molecular weights and narrow polydispersities; however, it comprehensive study of the end-group composition of the resulting polypeptides has not yet been performed. This reveals crucial information, as the end-groups are indicative of both the polymerization mechanism (i.e., initiation event) and the termination pathways. To this end, poly(O-benzyl-L-tyrosine) initiated by 1,6-diaminohexane was synthesized and Subsequently characterized by MALDI-TOF MS, NALDI-TOF MS, and (13)C NMR spectroscopy to ascertain the end-group structure. Polymers were prepared by both high-vacuum and glovebox techniques in DMF/THF. Preparation of poly(O-benzyl-L-tyrosine) by high-vacuum techniques yielded a polymer initiated exclusively by the normal amine mechanism, and termination by reaction with DMF was observed. In contrast, polymers prepared in the glovebox were initiated by the normal amine and activated monomer mechanisms, and several termination products arc evident. To our knowledge, this is the First rigorous and comparative analysis of the end-group structure, and it demonstrates the advantage of high-vacuum techniques for polymerization of NCAs for the preparation of well-defined polypeptides with end-group fidelity.
Περιγραφή
Λέξεις-κλειδιά
acid n-carboxyanhydrides, flight mass-spectrometry, light-scattering, capillary-electrophoresis, nca polymerization, block-copolymers, polypeptide, functionalization, chemistry, polymers
Θεματική κατηγορία
Παραπομπή
Σύνδεσμος
<Go to ISI>://000270807300025
http://pubs.acs.org/doi/pdfplus/10.1021/ma901340y
http://pubs.acs.org/doi/pdfplus/10.1021/ma901340y
Γλώσσα
en
Εκδίδον τμήμα/τομέας
Όνομα επιβλέποντος
Εξεταστική επιτροπή
Γενική Περιγραφή / Σχόλια
Ίδρυμα και Σχολή/Τμήμα του υποβάλλοντος
Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Μηχανικών Επιστήμης Υλικών