title: Recent Developments in the Synthesis of Biomacromolecules and their Conjugates by Single Electron Transfer-Living Radical Polymerization.
abstract: Single electron transfer-living radical polymerization (SET-LRP) represents a robust and versatile tool for the synthesis of vinyl polymers with well-defined topology and chain end functionality. The crucial step in SET-LRP is the disproportionation of the Cu(I)X generated by activation with Cu(0) wire, powder, or nascent Cu(0) generated in situ into nascent, extremely reactive Cu(0) atoms and nanoparticles and Cu(II)X2. Nascent Cu(0) activates the initiator and dormant chains via a homogeneous or heterogeneous outer-sphere single-electron transfer mechanism (SET-LRP). SET-LRP provides an ultrafast polymerization of a plethora of monomers (e.g., (meth)-acrylates, (meth)-acrylamides, styrene, and vinyl chloride) including hydrophobic and water insoluble to hydrophilic and water soluble. Some advantageous features of SET-LRP are (i) the use of Cu(0) wire or powder as readily available catalysts under mild reaction conditions, (ii) their excellent control over molecular weight evolution and distribution as well as polymer chain ends, (iii) their high functional group tolerance allowing the polymerization of commercial-grade monomers, and (iv) the limited purification required for the resulting polymers. In this Perspective, we highlight the recent advancements of SET-LRP in the synthesis of biomacromolecules and of their conjugates.
authors.affiliation: Roy & Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.|Laboratory of Sustainable Polymers, Department of Analytical Chemistry and Organic Chemistry, University Rovira i Virgili , Tarragona, Spain.
authors.forename: Gerard
authors.initials: G
authors.lastname: Lligadas
authors.affiliation: Roy & Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.
authors.forename: Silvia
authors.initials: S
authors.lastname: Grama
authors.affiliation: Roy & Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.
authors.forename: Virgil
authors.identifier: 0000-0001-5926-0489
authors.initials: V
authors.lastname: Percec
mesh_terms: D000178:Acrylamides / Q000737:chemistry; D000179:Acrylates / Q000737:chemistry; D003300:Copper / Q000737:chemistry; D004579:Electron Transport; D004583:Electrons; D057927:Hydrophobic and Hydrophilic Interactions; D046911:Macromolecular Substances / Q000138:chemical synthesis*; D008970:Molecular Weight; D053758:Nanoparticles / Q000737:chemistry; D058105:Polymerization; D020058:Styrene / Q000737:chemistry; D014753:Vinyl Compounds / Q000737:chemistry; D014867:Water / Q000737:chemistry
chemical_list: D000178:Acrylamides; D000179:Acrylates; D046911:Macromolecular Substances; D014753:Vinyl Compounds; D014867:Water; D020058:Styrene; D003300:Copper