Heteroleptic Copper(I) Complexes with Pyridine-Benzothiazole Ligands as Photocatalysts for Free Radical Photopolymerization and 3D Printing DOI
Naralyne M. Pesqueira,

Fabrice Morlet‐Savary,

Michael Schmitt

et al.

ACS Applied Polymer Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 6, 2025

Copper(I) complexes have attracted considerable attention as efficient redox photocatalysts (PCs) in photopolymerization. In this study, two copper(I) bearing a pyridine-benzothiazole ligand were thoroughly investigated for the free radical photopolymerization of ethoxylated trimethylolpropane triacrylate under violet and green light irradiation. A three-component system comprising copper complex, di-tert-butyl-diphenyl iodonium hexafluorophosphate, ethyl dimethylaminobenzoate additives was various conditions. The exhibited remarkable photoinitiation capabilities, achieving high monomer conversion rates highlighting significant structure–reactivity relationships. Based on energy calculations spectroscopic analyses, mechanistic pathway proposed. optimal conditions successfully applied 3D printing, producing smooth uniform structures.

Language: Английский

Photocontrolled RAFT polymerization: past, present, and future DOI Creative Commons

Yungyeong Lee,

Cyrille Boyer, Min Sang Kwon

et al.

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(9), P. 3035 - 3097

Published: Jan. 1, 2023

In this review, we provide a brief history, progress, and applications, discuss the remaining challenges of photocontrolled reversible addition-fragmentation chain transfer (RAFT) polymerization (i.e., photoinduced electron/energy transfer-RAFT (PET-RAFT), photoiniferter, photomediated cationic RAFT polymerization). Among these, visible-light-driven has attracted particular attention in recent years due to its benefits, including low energy consumption safe reaction procedure. Moreover, incorporation visible-light photocatalysis conferred attractive features, such as spatiotemporal control oxygen tolerance; however, clear understanding mechanism not been completely provided. We also present research efforts elucidate mechanisms with aid quantum chemical calculations combined experimental evidence. This review offers an insight into better design systems for desired applications helps realize full potential both academic- industrial-scale applications.

Language: Английский

Citations

144
Bulk depolymerization of poly(methyl methacrylate) via chain-end initiation for catalyst-free reversion to monomer DOI Creative Commons
James B. Young, Rhys W. Hughes,

A. Tamura

et al.

Chem, Journal Year: 2023, Volume and Issue: 9(9), P. 2669 - 2682

Published: Aug. 7, 2023

Language: Английский

Citations

78
Red-Light-Driven Atom Transfer Radical Polymerization for High-Throughput Polymer Synthesis in Open Air DOI Creative Commons
Xiaolei Hu, Grzegorz Szczepaniak, Anna Lewandowska-Andrałojć

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(44), P. 24315 - 24327

Published: Oct. 25, 2023

Photoinduced reversible-deactivation radical polymerization (photo-RDRP) techniques offer exceptional control over polymerization, providing access to well-defined polymers and hybrid materials with complex architectures. However, most photo-RDRP methods rely on UV/visible light or photoredox catalysts (PCs), which require multistep synthesis. Herein, we present the first example of fully oxygen-tolerant red/NIR-light-mediated photoinduced atom transfer (photo-ATRP) in a high-throughput manner under biologically relevant conditions. The method uses commercially available methylene blue (MB+) as PC [X-CuII/TPMA]+ (TPMA = tris(2-pyridylmethyl)amine) deactivator. mechanistic study revealed that MB+ undergoes reductive quenching cycle presence TPMA ligand used excess. formed semireduced MB (MB•) sustains by regenerating [CuI/TPMA]+ activator together provides polymerization. This dual catalytic system exhibited excellent oxygen tolerance, enabling polymerizations high monomer conversions (>90%) less than 60 min at low volumes (50-250 μL) synthesis library DNA-polymer bioconjugates narrow molecular weight distributions (Đ < 1.30) an open-air 96-well plate. In addition, broad absorption spectrum allowed ATRP be triggered UV NIR irradiation (395-730 nm). opens avenues for integration orthogonal reactions. Finally, MB+/Cu catalysis showed good biocompatibility during cells, expands potential applications this method.

Language: Английский

Citations

58
Visible‐Light‐Mediated Controlled Radical Branching Polymerization in Water DOI Creative Commons
Kriti Kapil, Grzegorz Szczepaniak, Michael R. Martinez

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(10)

Published: Jan. 16, 2023

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 situ from commercially available 2-bromoacrylic acid and used as a water-soluble inibramer to induce branching during copolymerization of methacrylate monomers. As result, well-defined branched obtained less than 30 min with predetermined molecular weights (36 000

Language: Английский

Citations

49
Current status and outlook for ATRP DOI Creative Commons
Krzysztof Matyjaszewski

European Polymer Journal, Journal Year: 2024, Volume and Issue: 211, P. 113001 - 113001

Published: March 30, 2024

Atom transfer radical polymerization (ATRP) is one of the most often used controlled techniques. It employs very small amounts (ppm) Cu complexes in presence various chemical reducing agents but also external stimuli such as light, electrical current or mechanical forces. can be carried out bulk, solution, and dispersed media. ATRP has been successfully to prepare polymers with architecture well-defined topology, composition, functionality, well bioconjugates organic–inorganic hybrids. This article summarizes status an outlook for ATRP.

Language: Английский

Citations

23
Robust Miniemulsion PhotoATRP Driven by Red and Near-Infrared Light DOI Creative Commons
Xiaolei Hu, Rongguan Yin, Jaepil Jeong

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(19), P. 13417 - 13426

Published: May 1, 2024

Photoinduced polymerization techniques have gathered significant attention due to their mild conditions, spatiotemporal control, and simple setup. In addition homogeneous media, efforts been made implement photopolymerization in emulsions as a practical greener process. However, previous photoinduced reversible deactivation radical (RDRP) heterogeneous media has relied on short-wavelength lights, which limited penetration depth, resulting slow relatively poor control. this study, we demonstrate the first example of highly efficient miniemulsion ATRP open air driven by red or near-infrared (NIR) light. This was facilitated utilization water-soluble photocatalyst, methylene blue (MB+). Irradiation red/NIR light allowed for excitation MB+ subsequent photoreduction deactivator presence electron donors initiate mediate The NIR light-driven photoATRP provided successful synthesis polymers with low dispersity (1.09 ≤ Đ 1.29) quantitative conversion within an hour. study further explored impact kinetics reactors varying sizes large-scale reaction (250 mL), highlighting advantages longer-wavelength light, particularly dispersed owing its superior penetration. work opens new avenues robust emulsion techniques, offering more approach improved control efficiency.

Language: Английский

Citations

19
Atom transfer radical polymerization DOI
Simon Harrisson, Richard Whitfield, Athina Anastasaki

et al.

Nature Reviews Methods Primers, Journal Year: 2025, Volume and Issue: 5(1)

Published: Jan. 9, 2025

Language: Английский

Citations

5
Oxygen, Light, and Mechanical Force Mediated Radical Polymerization Toward Precision Polymer Synthesis DOI
Zhujun Huang, Jin Dong, Kaiwen Liu

et al.

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This article highlights the advancements in controlled radical polymerization facilitated by three external regulations of oxygen, light, and mechanical force, outlines future directions polymerization.

Language: Английский

Citations

3
Oxygen-Driven Atom Transfer Radical Polymerization DOI

Yuxuan Du,

Zhe Chen,

Zhikang Xie

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 16, 2025

In traditional atom transfer radical polymerization (ATRP), oxygen must be meticulously eliminated due to its propensity quench species and halt the process. Additionally, oxidizes lower-valent Cu catalyst, compromising ability activate alkyl halides propagate polymerization. this study, we present an oxygen-driven ATRP utilizing alkylborane compounds, a method that not only circumvents need for stringent removal but also exploits as essential cofactor promote This approach exhibits broad compatibility in organic or aqueous media, yielding well-defined polymers with low dispersity (Đ 1.11) molecular weights closely aligned theoretical values. Triethylborane (Et3B) air-stable triethylborane-amine complex (Et3B-DMAP) facilitate controlled under open-to-air conditions, demonstrating efficiency across wide range of monomers. Moreover, technique enables successful synthesis protein–polymer conjugates supports surface modifications nanoparticles silicon wafers aerobic conditions. represents robust versatile platform precision far-reaching implications materials science, biomedicine, advanced engineering.

Language: Английский

Citations

3
Light-accelerated depolymerization catalyzed by Eosin Y DOI Creative Commons
Valentina Bellotti, Kostas Parkatzidis, Hyun Suk Wang

et al.

Polymer Chemistry, Journal Year: 2022, Volume and Issue: 14(3), P. 253 - 258

Published: Dec. 20, 2022

Retrieving the starting monomers from polymers synthesized by reversible deactivation radical polymerization has recently emerged as an efficient way to increase recyclability of such materials and potentially enable their industrial implementation. To date, most methods have primarily focused on utilizing high temperatures (typically 120 °C 180 °C) trigger depolymerization reaction. In this work, we show that, in presence Eosin Y under light irradiation, a much faster made addition-fragmentation chain-transfer (RAFT) can be triggered even at lower temperature (

Language: Английский

Citations

72