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

Chemical Science, Journal Year: 2022, Volume and Issue: 13(39), P. 11540 - 11550

Published: Jan. 1, 2022

Photoinduced atom transfer radical polymerization (photo-ATRP) has risen to the forefront of modern polymer chemistry as a powerful tool giving access 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 synthesis biohybrids. Herein, inspired by photoinduced electron transfer-reversible addition-fragmentation chain (PET-RAFT) polymerization, we demonstrate dual photoredox/copper catalysis that allows open-air ATRP green irradiation. Eosin Y was used an organic photoredox catalyst (PC) combination copper (X-Cu

Language: Английский

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Oxygen, Light, and Mechanical Force Mediated Radical Polymerization Toward Precision Polymer Synthesis

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

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Controlling Radical Polymerization with Biocatalysts

Macromolecules, Journal Year: 2023, Volume and Issue: 56(3), P. 751 - 761

Published: Feb. 3, 2023

Reversible deactivation radical polymerization (RDRP) is a set of powerful and versatile methods for the synthesis well-defined polymers. Over past two decades, engagement biocatalysts, namely, enzymes bacteria, has granted distinctive features to RDRP propelled toward more sustainable future. In this Perspective, we highlight green conditions, oxygen tolerance, function, ability access difficult polymers in conducted by biocatalysis (bio-RDRP), discuss major considerations when conducting bio-RDRP, point out drawbacks bottlenecks that limit its further development. The future bio-RDRP may benefit from expanding biocatalyst library, improving redox potential enhancing robustness, in-depth mechanistic studies.

Language: Английский

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Photo‐RAFT Polymerization for Hydrogel Synthesis through Barriers and Development of Light‐Regulated Healable Hydrogels under NIR Irradiation

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(25)

Published: March 29, 2023

We report an aqueous and near-infrared (NIR) light mediated photoinduced reversible addition-fragmentation chain transfer (photo-RAFT) polymerization system catalyzed by tetrasulfonated zinc phthalocyanine (ZnPcS4- ) in the presence of peroxides. Taking advantage its fast rates high oxygen tolerance, this is successfully applied for preparation hydrogels. Exploiting enhanced penetration NIR light, gelation effectively performed through non-transparent biological barriers. Notably, RAFT agents embedded these hydrogel networks can be reactivated on-demand, enabling healing under irradiation. In contrast to minimal capability (<15 %) hydrogels prepared free radical (FRP), RAFT-mediated display more than 80 % recovery tensile strength. Although healable polymer UV blue lights have already been established, work first photochemistry using facilitating thick

Language: Английский

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Photocontrolled radical polymerization for the synthesis of ultrahigh-molecular-weight polymers

Nature Synthesis, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 10, 2025

Language: Английский

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Oxygen-Driven Atom Transfer Radical Polymerization

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

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An Atom‐Economic Enzymatic Cascade Catalysis for High‐Throughput RAFT Synthesis of Ultrahigh Molecular Weight Polymers

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(46)

Published: Sept. 24, 2022

Abstract High‐throughput synthesis of well‐defined, ultrahigh molecular weight (UHMW) polymers by green approaches is highly desirable but remains unexplored. We report the creation an atom‐economic enzymatic cascade catalysis, consisting formate oxidase (FOx) and horseradish peroxidase (HRP), that enables high‐throughput reversible addition‐fragmentation chain transfer (RAFT) UHMW at volumes down to 50 μL. FOx transforms formic acid, a C 1 substrate, oxygen CO 2 H O , respectively. can escape from solution while harnessed in situ HRP generate radicals acetylacetone for RAFT polymerization, leaving no waste accumulation solution. Oxygen‐tolerant polymerization using redox cycles was successfully performed vials 96‐well plates produce libraries well‐defined polymers, represents first example method such materials extremely low volumes.

Language: Английский

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Degradable Block Copolymer Nanoparticles Synthesized by Polymerization‐Induced Self‐Assembly

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(12)

Published: Dec. 29, 2023

Abstract Polymerization‐induced self‐assembly (PISA) combines polymerization and in situ of block copolymers one system has become a widely used method to prepare copolymer nanoparticles at high concentrations. The persistence polymers the environment poses huge threat ecosystem represents significant waste resources. There is an urgent need develop novel chemical approaches synthesize degradable polymers. To meet with this demand, it crucial install degradability into PISA nanoparticles. Most recently, have been synthesized by introducing degradation mechanisms either shell‐forming or core‐forming blocks. This Minireview summarizes development PISA, including shell‐degradable, core‐degradable, all‐degradable Future will benefit from expansion techniques new adaptation high‐throughput for both syntheses studies.

Language: Английский

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Initiator‐Activation Strategy‐Enabled Organocatalyzed Reversible‐Deactivation Radical Polymerization Driven by Light

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(27)

Published: May 5, 2023

Organocatalyzed reversible-deactivation radical polymerizations (RDRPs) are attractive for many applications. Here, we developed photoredox-mediated RDRP by activating (hetero)aryl sulfonyl chloride (ArSO2 Cl) initiators with pyridines and designing a novel bis(phenothiazine)arene catalyst. The in situ formed pyridinium intermediates effectively promote controlled chain-growth from ArSO2 Cl, enabling access to various well-defined polymers high initiation efficiencies dispersities under mild conditions. This versatile method allows "ON/OFF" temporal control, chain-extension, facile synthesis of different polymer brushes via organocatalyzed grafting reactions linear chains. Time-resolved fluorescence decay studies calculations support the reaction mechanism. work provides transition-metal-free tailor readily available aromatic initiators, will design polymerization leveraged photoredox catalysis.

Language: Английский

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Aerobic-Controlled Radical Polymerization: Full Oxygen Tolerance Enabled by Air-Stable Amine–Borane

Macromolecules, Journal Year: 2024, Volume and Issue: 57(9), P. 4192 - 4198

Published: April 22, 2024

Conducting controlled radical polymerization (CRP) under ambient conditions presents a formidable challenge due to the efficient radical-quenching nature of molecular oxygen. Herein, we address inherent challenges by employing air-stable amine–borane complexes designed operate efficiently in presence These initiators demonstrate selective activation mild thermal or water, releasing active radicals for polymerization. Forming with diverse amines, these compounds are accessible and exist various forms from crystalline solids low-viscosity liquids. Rapid acrylamides acrylates an open-air environment without external deoxygenation yields well-defined polymers low dispersity, high monomer conversion, end-group fidelity. The minimum initiation temperature can be finely tuned over broad range selecting different organic media. Significantly, fully oxygen-tolerant also carried out at room aqueous media relying on stimuli. In addition, high-throughput synthesis series thermosensitive copolymers was performed using this aerobic CRP process order quickly investigate relationship between polymeric structure lower critical solution (LCST) property. This simple, robust, versatile approach may offer new opportunities application environments.

Language: Английский

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