Designer Template Initiator for Sequence Regulated Polymerization: Systems Design for Substrate‐Selective Metal‐Catalyzed Radical Addition and Living Radical Polymerization

Abstract

"Template initiator"' platforms (1) have been designed for expressing the sequence information in a template in radical polymerization. Thus, we demonstrated the structural adequacy of 1 consisting of two initiating sites placed ortho to each other in benzene: one for living cationic polymerization to introduce a template carrying substrate-recognition tags, and the other for metal-catalyzed living radical polymerization to achieve sequence regulation. For example, for two positional isomers with an amine template for an acid monomer, only the ortho initiator induced selective radical addition of MAA (recognizable) over MMA (non-recognizable). Another version was an oligo(vinyl ether) with a multiple amine template, which demonstrated template effects for MAA recognition over BzMA in copolymerization.

Sequence‐Controlled Multiblock Copolymers via RAFT Polymerization: Modeling and Simulations

“…However, it remains a difficult challenge to manipulate single chains and control the precise order of monomer units along the chain. Recent progress with regards to regulation of monomer sequences have been made via various approaches, including the use of low MW templates that anchors three monomer units in a specific sequence, selective radical additions of monomers using template initiators with recognition moieties, and approaches based on single addition of a monomer with low tendency toward homopolymerization, and a DNA‐templated approach . A recent biomimetic approach based on templated radical polymerization in nanoreactors also has potential with regards to manipulation of single chains …”

Prognostic significance of immunophenotypic and karyotypic features of Philadelphia positive B‐lymphoblastic leukemia in the era of tyrosine kinase inhibitors

“…Amphiphilic block copolymers consisting of hydrophilic and hydrophobic blocks have attracted considerable attentions1 and are widely used in various fields such as bioengineering,2, 3 nanotechnology,4, 5 and supramolecular science 6. Living/controlled radical polymerization (LRP) has become an established method to prepare well‐defined and novel functional amphiphilic copolymers with controlled molecular weights and molecular weight distribution 7–13. There are several distinct LRP techniques: atom transfer radical polymerization,14–17 reversible addition‐fragmentation chain transfer,18, 19 and nitroxide‐mediated polymerization (NMP) 20–23.…”

Controlled Alternating Copolymerization of (Meth)acrylates and Vinyl Ethers by Using Organoheteroatom‐Mediated Living Radical Polymerization

“…Such macromolecules would lead to the development of new polymeric materials with improved or novel properties. Although living radical polymerization (LRP) has become an indispensable method for the synthesis of structurally well‐controlled polymers with respect to molecular weights and molecular weight distributions with various functional groups,1–11 controlling the monomer sequence has been a formidable challenge 12–14. Alternating copolymerization occurs with certain combinations of monomer pairs under conventional radical polymerization conditions 15–20.…”