Peptide-polymer bioconjugates: hybrid block copolymers generated via living radical polymerizations from resin-supported peptides

Abstract

A novel strategy for the preparation of peptidic-synthetic bioconjugate block copolymers is based upon sequential condensation and living radical addition polymerizations, each performed upon a solid support.

Activators Regenerated by Electron Transfer for Atom‐Transfer Radical Polymerization of (Meth)acrylates and Related Block Copolymers

“…[8][9][10] It has been very successfully applied to the preparation of many nanocomposites, hybrids, and bioconjugates. [11][12][13][14][15][16][17][18][19][20][21][22][23] The advantages of ATRP, in comparison with other CRP processes, include the large range of available monomers and (macro)initiators, the simplicity of reaction setup, and the ability to conduct the process over a large range of temperatures, solvents, and dispersed media. [6,7,24] ATRP (Scheme 1) is a repetitive atom-transfer process between a macromolecular alkyl halide P n ÀX and a redoxactive transition-metal complex Cu I ÀX/ligand in which P n C radicals propagate (rate constant of propagation k p ) and are reversibly formed (rate constants k a and k da ).…”

Biological–synthetic hybrid block copolymers: Combining the best from two worlds

“…39 A second divergent strategy that has been recently introduced involves the solid-phase synthesis of the desired peptide sequence followed by controlled radical polymerization with the resin-bound peptide as the initiator. 41,42 A general overview of this strategy is presented in Scheme 11. Following this route, Wooley et al 41 first assembled an oligopeptide representing the protein transduction domain (PTD) of the HIV-1 TAT protein and extended this sequence with four additional glycine repeats with standard Fmoc solid-phase chemistry.…”

“…41,42 A general overview of this strategy is presented in Scheme 11. Following this route, Wooley et al 41 first assembled an oligopeptide representing the protein transduction domain (PTD) of the HIV-1 TAT protein and extended this sequence with four additional glycine repeats with standard Fmoc solid-phase chemistry. Next, the N-terminal amine group of the resin-bound peptide was functionalized with a fluorinated alkoxyamine derivative, which could act as an initiator for nitroxide-mediated radical polymerizations (NMPs).…”

Solid Phase Synthesis of Lysine-exposed Peptide-Polymer Hybrids by Atom Transfer Radical Polymerization

“…8,9 Many examples of hybrid block copolymers composed of a nano-biological segment, proteins, and one or two homopolypeptide sequences were reported. [10][11][12] Recently, the interest of utilizing the peptide-polymer hybrid materials (PPs) increased as building blocks, which could be assembled into nano-structures in selective solvents. [13][14][15][16] Recent advances in polymer synthesis, particularly in the field of controlled/living radical polymerization (CRP) techniques, such as atom transfer radical polymerization (ATRP), nitroxide-mediated polymerization (NMP), and reversible addition-fragmentation chain transfer (RAFT), stimulated the development of novel well-defined polymer-based bioconjugates.…”

“…20 The peptide-polymer hybrid materials were synthesized by the ATRP from resin-supported peptides by Washburn et al, 21 and the peptide-polymer bioconjugate block copolymers through the nitroxide-mediated radical polymerization (NMRP) from a solid support was shown by Wooley group. 12 In this study, we described our strategy to prepare the peptide-polymer hybrid materials by combining ATRP method with solid phase peptide synthesis. The standard solid phase peptide synthesis method was used to prepare the peptide.…”