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

Chemical Science, Год журнала: 2022, Номер 13(39), С. 11540 - 11550

Опубликована: Янв. 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

Язык: Английский

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

Chemical Communications, Год журнала: 2025, Номер unknown

Опубликована: Янв. 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.

Язык: Английский

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Oxygen-Driven Atom Transfer Radical Polymerization

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 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.

Язык: Английский

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Controlling Radical Polymerization with Biocatalysts

Macromolecules, Год журнала: 2023, Номер 56(3), С. 751 - 761

Опубликована: Фев. 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.

Язык: Английский

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

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(12)

Опубликована: Дек. 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.

Язык: 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, Год журнала: 2022, Номер 61(46)

Опубликована: Сен. 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.

Язык: 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, Год журнала: 2023, Номер 62(25)

Опубликована: Март 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

Язык: Английский

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

Nature Synthesis, Год журнала: 2025, Номер unknown

Опубликована: Янв. 10, 2025

Язык: Английский

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Nanozymes with Modulable Inhibition Transfer Pathways for Thiol and Cell Identification

Analytical Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 13, 2025

The elementary mechanism and site studies of nanozyme-based inhibition reactions are ambiguous urgently require advanced nanozymes as mediators to elucidate the effect. To this end, we develop a class featuring single Cu–N catalytic configurations B–O sites binding on porous nitrogen-doped carbon substrate (B6/CuSA) for inducing modulable transfer at atomic level. full redistribution electrons across sites, induced by incorporation, yields B6/CuSA with enhanced peroxidase-like activity versus CuSA. More importantly, CuSA features in cysteine expresses competitive through coordination bonds, an constant 0.048 mM. Benefiting from way nanozymes, possesses mixed approaches noncovalent bonds delivers record-mixed interaction 0.054 mM noncompetitive 0.71 Based CuSA, multichannel sensor array accomplishes detection various cancer cells, normal thiols. design principle work is endowed guidelines preliminary evaluation massive potential thiols, cell discrimination, disease prediction.

Язык: Английский

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Synthesis of Star Polymers with Ultrahigh Molecular Weights and Tunable Dispersities via Photoiniferter Polymerization

ACS Macro Letters, Год журнала: 2025, Номер unknown, С. 306 - 312

Опубликована: Фев. 21, 2025

Simultaneous control over macromolecular chain topology, molecular weight, and dispersity is an important synthetic goal in polymer chemistry. The synthesis of well-defined poly(methyl acrylate) star polymers with ultrahigh weights (>106 g mol-1) tunable dispersities realized for the first time via blue light-controlled photoiniferter polymerization using a tetrafunctional switchable RAFT agent (SRA4). spectroscopic properties activity SRA4 can be reversibly tuned by addition acid/base. For example, protonation 4-toluenesulfonic acid (TsOH) leads to enhanced UV-visible light absorption, faster rate, lower resulting polymer. Star were prepared predicted (Mn ≈ 80-1550 kg (Đ 1.8-1.2) when targeting degrees range 1000-20000 presence varying amounts TsOH. High end-group fidelity such was confirmed one-pot extension experiments, which afforded series pseudoblock copolymers controlled dispersities. Finally, rotational rheology used examine effect dispersity, topology (whether linear or star-shaped) on solution viscosity.

Язык: Английский

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