Adv Polym Sci (2013) 262: 1–38
DOI: 10.1007/12_2013_234
© Springer-Verlag Berlin Heidelberg 2013
Published online: 20 October 2013
Synthesis and Self-Assembly of Well-Defined
Block Copolypeptides via Controlled NCA
Polymerization
Timothy J. Deming
Abstract This article summarizes advances in the synthesis of well-defined polypeptides and block copolypeptides. Traditional methods used to polymerize α-amino
acid-N-carboxyanhydrides (NCAs) are described, and limitations in the utility of
these systems for the preparation of polypeptides are discussed. Improved initiators
and methods that allow polypeptide synthesis with good control over chain length,
chain length distribution, and chain-end functionality are also discussed. Using these
methods, block and random copolypeptides of controlled dimensions (including
molecular weight, sequence, composition, and molecular weight distribution) can
now be prepared. The ability of well-defined block copolypeptides to assemble into
supramolecular copolypeptide micelles, copolypeptide vesicles, and copolypeptide
hydrogels is described. Many of these assemblies have been found to possess
unique properties that are derived from the amino acid building blocks and ordered
conformations of the polypeptide segments.
Keywords Block copolypeptide Á Living polymerization Á N-Carboxyanhydride Á
Polypeptide Á Self assembly
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2 Polypeptide Synthesis Using NCAs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1 Conventional Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.2 Initiators for Transition Metal Catalysis . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . 6
2.3 Recent Developments Using Amine Initiators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
T.J. Deming (*)
Department of Bioengineering, University of California, 5121 Engineering 5, Los Angeles, CA
90095, USA
e-mail: demingt@seas.ucla.edu
DOI: 10.1007/12_2013_234
© Springer-Verlag Berlin Heidelberg 2013
Published online: 20 October 2013
Synthesis and Self-Assembly of Well-Defined
Block Copolypeptides via Controlled NCA
Polymerization
Timothy J. Deming
Abstract This article summarizes advances in the synthesis of well-defined polypeptides and block copolypeptides. Traditional methods used to polymerize α-amino
acid-N-carboxyanhydrides (NCAs) are described, and limitations in the utility of
these systems for the preparation of polypeptides are discussed. Improved initiators
and methods that allow polypeptide synthesis with good control over chain length,
chain length distribution, and chain-end functionality are also discussed. Using these
methods, block and random copolypeptides of controlled dimensions (including
molecular weight, sequence, composition, and molecular weight distribution) can
now be prepared. The ability of well-defined block copolypeptides to assemble into
supramolecular copolypeptide micelles, copolypeptide vesicles, and copolypeptide
hydrogels is described. Many of these assemblies have been found to possess
unique properties that are derived from the amino acid building blocks and ordered
conformations of the polypeptide segments.
Keywords Block copolypeptide Á Living polymerization Á N-Carboxyanhydride Á
Polypeptide Á Self assembly
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2 Polypeptide Synthesis Using NCAs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1 Conventional Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.2 Initiators for Transition Metal Catalysis . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . 6
2.3 Recent Developments Using Amine Initiators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
T.J. Deming (*)
Department of Bioengineering, University of California, 5121 Engineering 5, Los Angeles, CA
90095, USA
e-mail: demingt@seas.ucla.edu