Visible‐Light‐Mediated Controlled Radical Branching Polymerization in Water

Abstract

Hyperbranched polymethacrylates were synthesized by green‐light‐induced atom transfer radical polymerization (ATRP) under biologically relevant conditions in the open air. Sodium 2‐bromoacrylate (SBA) was prepared in situ from commercially available 2‐bromoacrylic acid and used as a water‐soluble inibramer to induce branching during the copolymerization of methacrylate monomers. As a result, well‐defined branched polymethacrylates were obtained in less than 30 min with predetermined molecular weights (36 000<Mn<170 000), tunable degree of branching, and low dispersity values (1.14≤Đ≤1.33). Moreover, the use of SBA inibramer enabled the synthesis of bioconjugates with a well‐controlled branched architecture.

Stochastic Simulation of Controlled Radical Polymerization Forming Dendritic Hyperbranched Polymers

“…Very recently, the application of the ATRP method in water using α-bromoacrylic acid as an evolmer was reported by Matyjaszewski. [31] The characteristic features of these reports are low Đs (Đ < 1.5), and the results contradicted our results. It should be noted that the Đs of HBPs, recently reported by Zhong using ATRP, were higher (Đ = 1.5-2.0) than their initial report when the conversion of the evolmer was high.…”

“…The same strategy for the structure control of HBPs based on atom transfer radical polymerization (ATRP) and reversible addition‐fragmentation‐chain transfer (RAFT) conditions was also reported by Zhong [29] and Chen, [30] in which α‐bromoacrylate and 1‐bromo‐1‐trifluoromethylethene were used as an evolmer, respectively. Very recently, the application of the ATRP method in water using α‐bromoacrylic acid as an evolmer was reported by Matyjaszewski [31] . The characteristic features of these reports are low Đ s ( Đ <1.5), and the results contradicted our results.…”

Synthesis of RNA-Amphiphiles via Atom Transfer Radical Polymerization in the Organic Phase

“…All the polymerization reactions in this study were performed using a recently developed photoinduced ATRP technique that is mediated by eosin Y (EYH 2 ) and copper catalyst under green light irradiation (Figure S7). , Due to its excellent oxygen tolerance and well-controlled polymerization behavior under physiological conditions, this technique allows polymerization using biomolecule initiators at low volume (i.e., 250 μL) without the deoxygenation processes . We have used this mild ATRP method successfully with DNA and also with RNA in the conventional approach to polymer hybrids.…”

Design of Microstructure-Engineered Polymers for Energy and Environmental Conservation

“…Architecture-engineered polymers beyond linear chains have emerged as a class of important materials in a broad spectrum of applications. In particular, branched polymers, including randomly (hyper)­branched or dendritic polymers, ,,, bottlebrush-like or graft polymers, − and star-shaped polymers, have been synthesized with high precision − ,,− and extensively studied to leverage the unique properties arising from their nonlinear intramolecular connections in the context of advanced environmental and energy materials. Although these different branched polymers afford properties that cannot be readily achieved in their linear counterparts, such as low viscosity, high end-group functionality, and reduced chain entanglement, the forms of intermolecular connections, i.e., topologies, and the degree of branching must be precisely controlled to access target material performance in specific applications.…”