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1. End‐To‐End FRET Enabling Direct Measurement of Oligomer Chain Conformations and Molecular Weight in Reaction Solutions

   https://doi.org/10.1002/marc.202400627  

   Valdez, Sara; Ismail, Syba; Wang, Yuming; Qiang, Zhe (January 2025, Macromolecular Rapid Communications)

   Abstract Förster resonance energy transfer (FRET) is an established tool for measuring distances between two molecules (donor and acceptor) on the nanometer scale. In the field of polymer science, the use of FRET to measure polymer end‐to‐end distances (R_ee) often requires complex synthetic steps to label the chain ends with the FRET pair. This work reports an anthracene‐functionalized chain‐transfer agent for reversible addition‐fragmentation chain‐transfer (RAFT) polymerization, enabling the synthesized chains to be directly end‐labeled with a donor and acceptor without the need for any post‐polymerization functionalization. Noteworthily, this FRET method allows for chain conformation measurements of low molecular weight oligomers in situ, without any work‐up steps. Using FRET to directly measure the averageR_eeof the oligomer chains during polymerization, the chain growth of methyl methacrylate, styrene, and methyl acrylate is investigated as a function of reaction time, including determining their degree of polymerization (DP). It is found thatDPresults from FRET are consistent with other established measurement methods, such as nuclear magnetic resonance (NMR) spectroscopy. Altogether, this work presents a broadly applicable and straightforward method to in situ characterizeR_eeof low molecular weight oligomers and theirDPduring reaction. 

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2. Achieving molecular weight distribution shape control and broad dispersities using RAFT polymerizations

   https://doi.org/10.1039/D1PY00399B  

   Rosenbloom, Stephanie I.; Sifri, Renee J.; Fors, Brett P. (January 2021, Polymer Chemistry)

   null (Ed.)

   Reversible addition–fragmentation chain-transfer (RAFT) polymerizations are one of the most versatile and powerful polymerization techniques for the synthesis of complex macromolecular architectures. While RAFT polymerizations often give polymers with narrow molecular weight distributions (MWDs), commodity plastics often have broad MWDs to give targeted properties and processability. Thus, new methods to precisely control both MWD breadth and shape are essential for fine-tuning polymer properties for next generation materials. Herein, we report a simple method for controlling polymer MWD features in thermally activated radical RAFT and redox activated cationic RAFT polymerizations by means of metered additions of chain transfer agents. 

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3. Open-air green-light-driven ATRP enabled by dual photoredox/copper catalysis

   https://doi.org/10.1039/D2SC04210J  

   Szczepaniak, Grzegorz; Jeong, Jaepil; Kapil, Kriti; Dadashi-Silab, Sajjad; Yerneni, Saigopalakrishna S.; Ratajczyk, Paulina; Lathwal, Sushil; Schild, Dirk J.; Das, Subha R.; Matyjaszewski, Krzysztof (October 2022, Chemical Science)

   Photoinduced atom transfer radical polymerization (photo-ATRP) has risen to the forefront of modern polymer chemistry as a powerful tool giving access to well-defined materials with complex architecture. However, most photo-ATRP systems can only generate radicals under biocidal UV light and are oxygen-sensitive, hindering their practical use in the synthesis of polymer biohybrids. Herein, inspired by the photoinduced electron transfer-reversible addition–fragmentation chain transfer (PET-RAFT) polymerization, we demonstrate a dual photoredox/copper catalysis that allows open-air ATRP under green light irradiation. Eosin Y was used as an organic photoredox catalyst (PC) in combination with a copper complex (X–Cu II /L). The role of PC was to trigger and drive the polymerization, while X–Cu II /L acted as a deactivator, providing a well-controlled polymerization. The excited PC was oxidatively quenched by X–Cu II /L, generating Cu I /L activator and PC˙ + . The ATRP ligand (L) used in excess then reduced the PC˙ + , closing the photocatalytic cycle. The continuous reduction of X–Cu II /L back to Cu I /L by excited PC provided high oxygen tolerance. As a result, a well-controlled and rapid ATRP could proceed even in an open vessel despite continuous oxygen diffusion. This method allowed the synthesis of polymers with narrow molecular weight distributions and controlled molecular weights using Cu catalyst and PC at ppm levels in both aqueous and organic media. A detailed comparison of photo-ATRP with PET-RAFT polymerization revealed the superiority of dual photoredox/copper catalysis under biologically relevant conditions. The kinetic studies and fluorescence measurements indicated that in the absence of the X–Cu II /L complex, green light irradiation caused faster photobleaching of eosin Y, leading to inhibition of PET-RAFT polymerization. Importantly, PET-RAFT polymerizations showed significantly higher dispersity values (1.14 ≤ Đ ≤ 4.01) in contrast to photo-ATRP (1.15 ≤ Đ ≤ 1.22) under identical conditions. 

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4. Photo‐Mediated RAFT Step‐Growth Polymerization With Diacrylate Monomers: Investigating Versatility and Oxygen Tolerance

   https://doi.org/10.1002/marc.202400602  

   Clouthier, Samantha Marie; Li, Jiajia; Tanaka, Joji; You, Wei (January 2025, Macromolecular Rapid Communications)

   Abstract Photomediated reversible addition fragmentation chain transfer (RAFT) step‐growth polymerization is performed using a trithiocarbonate‐based chain transfer agent (CTA) and acrylate‐based monomers both with and without a photocatalyst. The versatility of photo‐mediated RAFT step‐growth is demonstrated by one‐pot synthesis of a graft copolymer via sequential monomer addition. Furthermore, oxygen‐tolerant photo‐mediated RAFT step‐growth is demonstrated, facilitated by the appropriate selection of photocatalyst and solvent pair (zinc tetraphenyl porphyrin [ZnTPP] and dimethyl sulfoxide [DMSO]), enabling ultralow volume polymerization under open‐air conditions. 

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5. Radical–radical coupling effects in the direct-growth grafting-through synthesis of bottlebrush polymers using RAFT and ROMP

   https://doi.org/10.1039/d2py00794k  

   Alaboalirat, Mohammed; Vu, Clark; Matson, John B. (October 2022, Polymer Chemistry)

   The direct-growth technique was used to synthesize several macromonomers (MMs) employing reversible addition–fragmentation chain transfer (RAFT) polymerization by growing directly from a norbornene-functionalized chain transfer agent (CTA). We aimed to investigate the formation of bisnorbornenyl species resulting from radical termination by combination ( i.e. , coupling) during RAFT polymerization at different monomer conversion values in four types of monomers: styrene, tert -butyl acrylate, methyl methacrylate and N -acryloyl morpholine. Ring-opening metathesis polymerization (ROMP) of these MMs using Grubbs' 3rd generation catalyst (G3) at an MM : G3 ratio of 100 : 1 resulted in the formation of bottlebrush polymers. Analysis by size-exclusion chromatography (SEC) revealed high molar mass shoulders of varying intensities attributed to the incorporation of these bisnorbornenyl species to generate dimeric or higher-order bottlebrush polymer oligomers. The monomer type in the RAFT step heavily influenced the amount of these bottlebrush polymer dimers and oligomers, as did the monomer conversion value in the RAFT step: We found that the ROMP of polystyrene MMs with a target backbone degree of polymerization of 100 produced detectable coupling at ≥20% monomer conversion in the RAFT step, while it took ≥80% monomer conversion to observe coupling in the poly( tert -butyl acrylate) MMs. We did not detect coupling in the poly(methyl methacrylate) MMs, but broadening of the SEC peaks and an increase in dispersity occurred, suggesting the presence of metathesis-active alkene-containing chain ends created by disproportionation. Finally, poly( N -acryloyl morpholine) MMs, even when reaching 90% monomer conversion in the RAFT step, showed no detectable coupling in the bottlebrush polymers. These results highlight the importance of monomer choice and RAFT polymerization conditions in making MMs for ROMP grafting-through to make well-defined bottlebrush polymers. 

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