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

Photoinduced Organocatalyzed Atom Transfer Radical Polymerization (O-ATRP): Precision Polymer Synthesis Using Organic Photoredox Catalysis DOI Creative Commons
Daniel A. Corbin, Garret M. Miyake

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 1830 - 1874

Published: Nov. 29, 2021

The development of photoinduced organocatalyzed atom transfer radical polymerization (O-ATRP) has received considerable attention since its introduction in 2014. Expanding on many the advantages traditional ATRP, O-ATRP allows well-defined polymers to be produced under mild reaction conditions using organic photoredox catalysts. As a result, opened access range sensitive applications where use metal catalyst could concern, such as electronics, certain biological applications, and coordinating monomers. However, key limitations this method remain necessitate further investigation continue field. such, review details achievements made to-date well future research directions that will expand capabilities application landscape O-ATRP.

Language: Английский

Citations

226
Recent advances in nanocellulose processing, functionalization and applications: a review DOI Creative Commons

Vaishali Thakur,

Ashish Guleria, Sanjay Kumar

et al.

Materials Advances, Journal Year: 2021, Volume and Issue: 2(6), P. 1872 - 1895

Published: Jan. 1, 2021

Graphical presentation form synthesis to application of nanocellulose.

Language: Английский

Citations

201
The mechanochemical synthesis of polymers DOI Creative Commons
Annika Krusenbaum, Sven Grätz, Getinet Tamiru Tigineh

et al.

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(7), P. 2873 - 2905

Published: Jan. 1, 2022

Mechanochemistry enables solvent-free syntheses of even novel polymer structures without the need monomer solubility.

Language: Английский

Citations

196
Making ATRP More Practical: Oxygen Tolerance DOI
Grzegorz Szczepaniak, Liye Fu,

Hossein Jafari

et al.

Accounts of Chemical Research, Journal Year: 2021, Volume and Issue: 54(7), P. 1779 - 1790

Published: March 22, 2021

Atom-transfer radical polymerization (ATRP) is a well-known technique for the controlled of vinyl monomers under mild conditions. However, as with any other polymerization, ATRP typically requires rigorous oxygen exclusion, making it time-consuming and challenging to use by nonexperts. In this Account, we discuss various approaches achieving tolerance in ATRP, presenting overall progress field.Copper-mediated which first discovered late 1990s, uses CuI/L activator that reversibly reacts dormant C(sp3)-X polymer chain end, forming X-CuII/L deactivator propagating radical. Oxygen interferes activation propagation quenching radicals oxidizing activator. At equilibrium, present at much higher concentration than radicals. Thus, oxidation dominant inhibition pathway. conventional reaction irreversible, so must be strictly excluded achieve good results.Over last two decades, our group has developed several techniques based on concept regenerating When oxidized continuously converted back its active reduced form, then catalytic system itself can act an scavenger. Regeneration accomplished reducing agents photo-, electro-, mechanochemical stimuli. This family methods offers degree tolerance, but most them tolerate only limited amount do not allow open vessel.More recently, enzymes used auxiliary systems directly deoxygenate medium protect process. We method glucose oxidase (GOx), glucose, sodium pyruvate very effectively scavenge enable open-vessel ATRP. By adding second enzyme, horseradish peroxidase (HPR), managed extend role enzymatic generating carbon-based changed from oxygen-sensitive oxygen-fueled reaction.While performing control experiments methods, noticed using UV irradiation triggers without presence GOx. serendipitous discovery allowed us develop oxygen-proof, small-molecule-based, photoinduced system. It similar exhibits superior compatibility both aqueous media organic solvents, avoids problems associated purifying polymers enzymes. The was able rapidly polymerize N-isopropylacrylamide, monomer, high control.These contributions have substantially simplified more practical accessible everyone.

Language: Английский

Citations

159
Porphyrinic Zirconium Metal–Organic Frameworks (MOFs) as Heterogeneous Photocatalysts for PET‐RAFT Polymerization and Stereolithography DOI
Liwen Zhang, Xiaobing Shi,

Zhiheng Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(10), P. 5489 - 5496

Published: Nov. 12, 2020

Abstract In this study, porphyrinic zirconium (Zr) MOFs were investigated as heterogeneous photocatalysts for photoinduced electron transfer‐reversible addition‐fragmentation chain transfer (PET‐RAFT) polymerization of various monomers under a broad range wavelengths, producing polymers with high monomer conversions, narrow molecular weight distributions, low dispersity and good chain‐end fidelity. Screening Zr‐MOFs (Zn) containing Zn‐metalled ligands demonstrated that MOF‐525 the smallest size had best photocatalytic activity in PET‐RAFT polymerization, due to enhanced dispersion light penetration. Oxygen tolerance temporal control also during MOF catalysed PET‐RAFT. Results suggested rates significantly affected by changing surface area MOFs, could be easily separated recycled up five independent polymerizations without an obvious decrease efficiency. Finally, utilized create three‐dimensional polymeric objects resolution via visible mediated stereolithography open‐air environment.

Language: Английский

Citations

150
Mussel-inspired chemistry: A promising strategy for natural polysaccharides in biomedical applications DOI
Fangfei Liu, Xiong Liu, Feng Chen

et al.

Progress in Polymer Science, Journal Year: 2021, Volume and Issue: 123, P. 101472 - 101472

Published: Oct. 18, 2021

Language: Английский

Citations

140
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

140
Rapid High‐Resolution 3D Printing and Surface Functionalization via Type I Photoinitiated RAFT Polymerization DOI
Kenneth Lee, Nathaniel Corrigan, Cyrille Boyer

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(16), P. 8839 - 8850

Published: Jan. 15, 2021

Abstract RAFT facilitated digital light projection 3D printing of polymeric materials provides a convenient and facile route for inducing post‐fabrication transformations via reactivation dormant chain transfer agents. In this work, we report the use Norrish type I photoinitiator in conjunction with agent to produce variety open‐air printable resins that rapidly cure under visible irradiation. The photoinitiator‐RAFT system polymerizes extremely quickly high build rates up 9.1 cm h −1 , representing 7‐fold increase compared previous mediated systems. printed containing thiocarbonylthio groups can be also produced using low concentrations divinyl comonomers initial resins, which has not been successfully achieved other photocontrolled polymerization techniques. Interestingly, inclusion agents significantly improves resolution formulations without agent, allowing fabrication intricate complex objects. Spatiotemporally controlled surface modifications objects from on material surfaces were performed one two‐pass configurations, multiple successive post‐printing same object.

Language: Английский

Citations

121
Photo‐Iniferter RAFT Polymerization DOI Creative Commons
Matthias Hartlieb

Macromolecular Rapid Communications, Journal Year: 2021, Volume and Issue: 43(1)

Published: Nov. 9, 2021

Light-mediated polymerization techniques offer distinct advantages over reactions fueled by thermal energy, such as high spatial and temporal control well the possibility to work under mild reaction conditions. Reversible addition-fragmentation chain-transfer (RAFT) is a highly versatile radical method that can be utilized variety of monomers produce vast number complex macromolecular structures. The use light drive RAFT-polymerization possible via multiple routes. Besides photo-initiators, or photo-catalysts, direct activation chain transfer agent controlling RAFT process in photo-iniferter (PI) an elegant way initiate reactions. Within this review, PI-RAFT its conventional are discussed detail.

Language: Английский

Citations

119
Reversible Deactivation Radical Polymerization: From Polymer Network Synthesis to 3D Printing DOI Creative Commons
Ali Bagheri, Christopher M. Fellows, Cyrille Boyer

et al.

Advanced Science, Journal Year: 2021, Volume and Issue: 8(5)

Published: Jan. 21, 2021

Abstract 3D printing has changed the fabrication of advanced materials as it can provide customized and on‐demand networks. However, polymer with capacity to be transformed after remains a great challenge for engineers, material, scientists. Radical polymerization been conventionally used in photopolymerization‐based printing, broader context crosslinked Although this reaction pathway shown promise, offers limited control over chain growth, architecture, thus final properties More fundamentally, radical produces dead chains incapable postpolymerization transformations. Alternatively, application reversible deactivation (RDRP) networks allows tuning network homogeneity more importantly, enables production containing dormant reactivatable species that subsequent processes postsynthetic stage. Consequently, opportunities (photoactivated) RDRP‐based offer have leveraged through novel concepts structurally tailored engineered macromolecular gels, living additive manufacturing photoexpandable/transformable‐polymer Herein, advantages irreversibly formed conventional are discussed.

Language: Английский

Citations

118