End-group functionalization and postpolymerization modification of helical poly(isocyanide)s

Anna Croom, Rossella Tarallo, Marcus Weck

Research output: Contribution to journalArticle

Abstract

This contribution presents the synthesis of helical alkyne-terminated polymers using a functionalized Nickel complex to initiate the polymerization of menthylphenyl isocyanides. The resulting polymers display low dispersities and controlled molecular weights. Copper-catalyzed azide/alkyne cycloadditions (CuAAC) are performed to attach various azide-containing compounds to the polymer termini. After azido-phosphonate moiety attachment the polymer displays a signal at 25.4 ppm in the 31P NMR spectrum demonstrating successful end-group functionalization. End-group functionalization of a fluorescent dye allows to determine the functionalization yield as 89% (±8). Successful ligation of an azide-functionalized peptide sequence (MKLA=1547 g/mol) increases the Mn from 5100 for the parent polymer to 6700 for the bioconjugate as visualized by GPC chromatography. Analysis by CD spectroscopy confirms that the helical conformation of the poly(isocyanide) block in the peptide-polymer conjugate is maintained after postpolymerization modification. These results demonstrate an easy, generalizable, and versatile strategy toward mono-telechelic helical polymers.

Original languageEnglish (US)
Pages (from-to)2766-2773
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume54
DOIs
StatePublished - 2016

Fingerprint

Cyanides
Polymers
Azides
Alkynes
Peptides
Organophosphonates
Cycloaddition
Chromatography
Nickel
Fluorescent Dyes
Conformations
Copper
Dyes
Molecular weight
Polymerization
Nuclear magnetic resonance
Spectroscopy

Keywords

  • Anionic polymerization
  • Functionalization of polymers
  • Initiators
  • Peptide-functionalization
  • Telechelics

ASJC Scopus subject areas

  • Materials Chemistry
  • Polymers and Plastics
  • Organic Chemistry

Cite this

End-group functionalization and postpolymerization modification of helical poly(isocyanide)s. / Croom, Anna; Tarallo, Rossella; Weck, Marcus.

In: Journal of Polymer Science, Part A: Polymer Chemistry, Vol. 54, 2016, p. 2766-2773.

Research output: Contribution to journalArticle

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