Single-Electron Transfer Living Radical Polymerization Platform to Practice, Develop, and Invent

Abstract

The most fundamental aspects of single-electron transfer (SET) principles are presented. They are discussed according to different definitions used by expert practitioners and are applied to SET living radical polymerization (SET-LRP) according to the definition of the division of organic chemistry of IUPAC that relies on principles elaborated by Taube, Eberson, Chanon, and Kochi. Additional definitions are also discussed to help clarify for the nonexpert contradictory literature reports. Subsequently, the principles and evolution of SET-LRP together with the methodologies currently available to practice it are discussed. It is expected that this Perspective will be able to help experts and nonexperts practice, develop, and invent new concepts and methodologies for SET-LRP to advance its status and the status of other living radical polymerization methods to the level of the most precise living polymerization methods.

Ultrasound and Sonochemistry for Radical Polymerization: Sound Synthesis

“…The synthesis of aD NA-polymer biohybrid was carried out by using an alkyl halide-functionalized DNA fragment, indicating the potential for this sono-ATRP technique to be utilized for bio-conjugation reactions where aqueous conditions and ambient temperatures are often desirable. [94] By using ah igher operating frequency( f = 490 kHz), our group was able to achieve af aster polymerization rate under otherwise similar conditions. [92] This is attributed to the increased radical generation efficiency at higher ultrasonic frequencies.…”

SET-LRP in biphasic mixtures of fluorinated alcohols with water

“…Single-Electron Transfer Living Radical Polymerization (SET-LRP) is sustained by the self-regulated generation of the Cu(0) activator and Cu(II)X 2 /ligand deactivator via the solventligand mediated disproportionation of Cu(I)X species. [1][2][3][4][5][6][7][8] This fundamental step is known to occur not only in water but also in many polar organic solvents in the presence of N-donor ligands that preferentially bind Cu(II)X 2 rather than Cu(I)X. Hence, water, [9][10][11][12][13] dimethyl sulfoxide (DMSO), [14][15][16][17] dimethyl formamide (DMF), dimethyl acetamide (DMAC), ethylene carbonate, alcohols, [18][19][20][21][22][23][24][25] and some of their binary mixtures 12,26,27 are excellent reaction media to practice SET-LRP.…”

Fabrication of Polymer–Protein Hybrids

“…Single‐electron‐transfer living radical polymerization (SET‐LRP) is activated by a catalytic amount of the electron donor Cu(0) through a heterolytic outer sphere single‐electron‐transfer process. This method shows excellent control of molecular weight distribution, and perfect retention of chain‐end functionality . Haddleton and co‐workers successfully applied SET‐LRP in the synthesis of well‐defined thermoresponsive polymer–protein conjugates .…”

“…This method shows excellent control of molecular weight distribution, and perfect retention of chain-end functionality. [133][134][135][136] Haddleton and co-workers successfully applied SET-LRP in the synthesis of well-defined thermoresponsive polymer-protein conjugates. [137] Salmon calcitonin (sCT) was treated with tris(2-carboxyethyl)phosphine (TCEP), yielding two thiols available, and subsequently reacted with acrylic functional initiator.…”