☆ 4.5 Review

PET-RAFT polymerization under flow chemistry and surface-initiated reactions

POLYMER INTERNATIONAL (2023)

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Article Biochemistry & Molecular Biology

Versatile Bilayer Hydrogel for Wound Dressing through PET-RAFT Polymerization

Jianzhi Liu et al.

Summary: A bilayer hydrogel dressing model with an inner layer possessing antibacterial, thermoresponsive, and biocompatible properties, and an outer layer with good stretchability and toughness, was proposed. Experimental results demonstrated that the bilayer hydrogel dressing significantly accelerates wound healing.

BIOMACROMOLECULES (2022)

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Article Polymer Science

Synthesis of Hyperbranched Polymers via PET-RAFT Self-Condensing Vinyl Polymerization in a Flow Reactor

Li-Han Rong et al.

Summary: Photoinduced polymerization techniques, particularly combining RAFT with SCVP, were used to prepare hyperbranched polymers in a flow reactor under extremely mild conditions in this study. The use of a flow reactor showed improved scalability, reliability, and efficiency, allowing for the synthesis of block copolymers with considerable controllability in molecular weight and branching density by adjusting the feeding ratio of monomer to transmer.

MACROMOLECULAR CHEMISTRY AND PHYSICS (2022)

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Review Polymer Science

Photo-Iniferter RAFT Polymerization

Matthias Hartlieb

Summary: Light-mediated RAFT polymerization offers advantages such as high spatial and temporal control, versatility with various monomers, and operation under mild conditions. The use of light to drive the RAFT process is possible through multiple pathways, including direct activation of the chain transfer agent in a photo-iniferter process.

MACROMOLECULAR RAPID COMMUNICATIONS (2022)

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Article Polymer Science

Dual enhancement of carrier generation and migration on Au/g-C3N4 photocatalysts for highly-efficient broadband PET-RAFT polymerization

Mengya Li et al.

Summary: A novel photoinduced electron/energy transfer RAFT (PET-RAFT) polymerization method was developed using Au/g-C3N4 composite photocatalysts, which greatly enhanced the efficiency and control of the polymerization process.

POLYMER CHEMISTRY (2022)

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Article Polymer Science

One-Pot Synthesis of Amphiphilic Biopolymers from Oxidized Alginate and Self-Assembly as a Carrier for Sustained Release of Hydrophobic Drugs

Zhaowen Liu et al.

Summary: In this study, an organic solvent-free, eco-friendly and efficient approach for the preparation of amphiphilic conjugates (Ugi-OSAOcT) was developed by grafting octylamine to oxidized sodium alginate. The conjugates self-assembled into stable and spherical micelles and successfully loaded the poorly water-soluble drug ibuprofen. The loaded micelles exhibited sustained and pH-responsive drug release behavior.

POLYMERS (2022)

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Article Chemistry, Multidisciplinary

Diblock and Random Antifouling Bioactive Polymer Brushes on Gold Surfaces by Visible-Light-Induced Polymerization (SI-PET-RAFT) in Water

Andriy R. Kuzmyn et al.

Summary: Surface-initiated photoinduced electron-transfer-reversible addition-fragmentation chain transfer (SI-PET-RAFT) was utilized for the first time to create antifouling polymer brushes on gold surfaces. The polymerization process allowed for the production of random and diblock copolymer brushes, demonstrating excellent antifouling properties against undiluted human serum. The amount of bioactive moiety immobilization in the polymer brushes was analyzed with respect to brush structure, showing superior results in the diblock copolymer brush. This approach provides a scalable, robust, mild, oxygen-tolerant, and heavy-metal-free method for producing antifouling and functional copolymer brushes with potential applications in biosensing and tissue engineering.

ADVANCED MATERIALS INTERFACES (2022)

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Article Materials Science, Multidisciplinary

Fundamentals and Applications of Polymer Brushes in Air

Guido C. Ritsema van Eck et al.

Summary: This article summarizes the research on high-density, end-tethered polymers, also known as polymer brushes, in liquids and their applications in air. It discusses the fundamental concepts and various applications of brushes in air, and provides an outlook on the future large-scale application of brushes. The article also identifies open questions and issues that need to be addressed.

ACS APPLIED POLYMER MATERIALS (2022)

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Article Materials Science, Multidisciplinary

Self-Assembled Catalytic Nanoreactors from Molecular Brushes by Utilizing Postpolymerization Modification for Catalyst Attachment

Maolin Wang et al.

Summary: Polymer-based catalytic nanoreactors were successfully fabricated by self-assembly of molecular brushes, showing high catalytic activities towards organic transformations in water.

ACS APPLIED POLYMER MATERIALS (2022)

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Article Polymer Science

Anti-UV and hydrophobic dual-functional coating fabrication for flame retardant polyester fabrics by surface-initiated PET RAFT technique

Qiang Hu et al.

Summary: Inspired by living radical polymerization (LRP), surface-initiated LPR technology has great potential in controlling and tailoring polymer coatings. In this study, a surface-initiated photoinduced electron transfer-reversible addition-fragmentation chain transfer polymerization (SI-PET-RAFT) method was used to fabricate polymeric brushes with anti-UV and hydrophobic properties on flame retardant polyester fabrics (FRPET). The results showed that this method achieved controlled growth of polymeric brushes on the fabric surface, resulting in improved anti-UV, flame retardant, and hydrophobic properties.

EUROPEAN POLYMER JOURNAL (2022)

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Review Chemistry, Physical

Brush-Modified Hydrogels: Preparations, Properties, and Applications

Baoqi Wu et al.

Summary: Hydrogels with polymer brush architectures have been rapidly growing in recent years and show improved properties compared with classical hydrogels, making them increasingly employed in various fields including biomedical devices, tissue engineering, drug delivery, antifouling materials, and lubrication materials.

CHEMISTRY OF MATERIALS (2022)

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Article Polymer Science

PET-RAFT Increases Uniformity in Polymer Networks

Shiwanka V. Wanasinghe et al.

Summary: Photoinduced electron/energy transfer (PET) -reversible addition-fragmentation chain transfer polymerization (RAFT) and conventional photoinitiated RAFT were used to synthesize polymer networks. The PET-RAFT systems generated more uniform networks than those made by conventional RAFT, with the electron transfer-based catalytic pathway showing superior results.

ACS MACRO LETTERS (2022)

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Article Materials Science, Multidisciplinary

SI-PET-RAFT Polymerization via Electrodeposited Macroinitiator Thin Films: Toward Biomedical and Sensing Applications

Li-Han Rong et al.

Summary: Surface-initiated photoinduced electron transfer-reversible addition-fragmentation chain transfer (SI-PET-RAFT) polymerization is used to prepare polymer brushes on conductive surfaces. An electrochemically active carbazole-containing chain transfer agent is used as the macroinitiator, capable of mediating polymerization and forming block copolymers. The resulting polymer brush films can encapsulate colloidal gold nanoparticles, suggesting potential biomedical applications.

ACS APPLIED POLYMER MATERIALS (2022)

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Article Materials Science, Multidisciplinary

Superhydrophilic Polymer Brushes with High Durability and Anti-fogging Activity

Michele Fromel et al.

Summary: The study introduces a fully aqueous surface-initiated polymerization method for the formation of durable superhydrophilic polymer coatings. The approach utilizes water as a sole solvent and mild yellow light to improve durability and overcome traditional limitations related to monomer solubility and oxygen tolerance. Polymer films engineered through this method show promise as functional materials with enhanced durability, effectively combatting surface fogging challenges.

ACS APPLIED POLYMER MATERIALS (2021)

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Article Chemistry, Multidisciplinary

Porphyrinic Zirconium Metal-Organic Frameworks (MOFs) as Heterogeneous Photocatalysts for PET-RAFT Polymerization and Stereolithography

Liwen Zhang et al.

Summary: Porphyrinic zirconium (Zr) MOFs were used as heterogeneous photocatalysts for PET-RAFT polymerization, producing polymers with high efficiency, narrow molecular weight distributions, low dispersity, and good chain-end fidelity. MOF-525 (Zn) with the smallest size exhibited the best photocatalytic activity, and changing the size and surface area of MOFs significantly affected the polymerization rates. The MOF photocatalysts showed oxygen tolerance, temporal control, and could be easily separated and recycled for multiple PET-RAFT polymerizations without loss of efficiency.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

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Review Polymer Science

Hyperbranched Polymer-based Nanocomposites: Synthesis, Progress, and Applications

Matin Suraj Belgaonkar et al.

Summary: Hyperbranched polymer nanocomposites, based on unique 3D structure and high solvability of hyperbranched polymers, provide new opportunities and challenges in material science. These materials have wide applications in fields such as light-trapping, modification, and stabilization, highlighting the strong interactions between HBP matrices and nanofillers.

EUROPEAN POLYMER JOURNAL (2021)

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Article Chemistry, Multidisciplinary

Regulation of Proteins to the Cytosol Using Delivery Systems with Engineered Polymer Architecture

Jessica A. Kretzmann et al.

Summary: Modulation of surface functionality significantly affects overall delivery efficiency, while manipulation of polymer architecture can highly regulate endosomal release rate.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Review Polymer Science

Bottlebrush polymers: From controlled synthesis, self-assembly, properties to applications

Zili Li et al.

Summary: BBPs are a class of materials with excellent performance in various applications, and their structures can be controlled by manipulating chemical structures and compositions, showing great potential in a wide range of applications.

PROGRESS IN POLYMER SCIENCE (2021)

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Article Polymer Science

Synthesis of Polymer Brushes Via SI-PET-RAFT for Photodynamic Inactivation of Bacteria

Gervase Ng et al.

Summary: The authors present a facile method for preparing surface-tethered polymeric brushes with antifouling and visible light activated bactericidal properties. The brushes exhibit antibacterial properties by generating singlet oxygen, which can be temporally and spatially controlled, against both Gram-positive and Gram-negative bacteria. Additionally, the antibacterial properties of the surface are recyclable.

MACROMOLECULAR RAPID COMMUNICATIONS (2021)

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Article Polymer Science

Divergent Synthesis of Graft and Branched Copolymers through Spatially Controlled Photopolymerization in Flow Reactors

Nathaniel Corrigan et al.

Summary: This research demonstrates the controlled synthesis of graft and branched copolymers without intermediate purification using one-pot or one-pass processes. The formation of poly(methacrylate) copolymers with pendent reversible addition-fragmentation chain transfer (RAFT) agent functionalities was performed through selective photoactivation, followed by a nonselective photoinduced chain extension to provide tailored graft copolymers. By alternating the light sources, a range of macromolecular architectures could be prepared from the same starting materials, showing the versatility and flexibility of this approach.

MACROMOLECULES (2021)

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Article Polymer Science

PET-RAFT Polymerization: Mechanistic Perspectives for Future Materials

Michael L. Allegrezza et al.

Summary: In the past decade, photochemistry has become a growing area in organic and polymer chemistry, with the use of light to drive polymerization providing spatial and temporal control over the reaction. The mechanism of electron versus energy transfer in photoinduced polymerization processes like PET-RAFT is still debated in the literature, with conflicting reports on the underlying process. Different catalytic systems in PET-RAFT have unique characteristics, and there is no consensus in the current literature across all processes.

ACS MACRO LETTERS (2021)

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Review Polymer Science

New Light in Polymer Science: Photoinduced Reversible Addition-Fragmentation Chain Transfer Polymerization (PET-RAFT) as Innovative Strategy for the Synthesis of Advanced Materials

Valentina Bellotti et al.

Summary: The combination of photochemistry and reversible-deactivation radical polymerizations (RDRP) has attracted significant interest in the synthesis of innovative materials. Among the various techniques, Photoinduced Electron/Energy Transfer Reversible Addition-Fragmentation Chain-Transfer (PET-RAFT) polymerization stands out for its advantages in applicability, cost, and sustainability. This review aims to provide basic knowledge of PET-RAFT polymerization and explore its potential in industrial applications, new materials production, and environmental sustainability.

POLYMERS (2021)

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Article Polymer Science

User-friendly chemical patterning with digital light projection polymer brush photolithography

Michele Fromel et al.

Summary: This contribution introduces a robust topographical and chemical patterning platform utilizing an LED digital light projector and oxygen-tolerant light-mediated polymerization to design advanced surfaces on the micron scale in mild ambient conditions. The user-friendly nature of this approach aims to bring complex chemical patterning abilities based on surface-tethered polymers into the hands of non-experts, enabling fundamental and applied studies related to patterned surfaces in bioengineering.

EUROPEAN POLYMER JOURNAL (2021)

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Article Polymer Science

Muttipath oxygen-mediated PET-RAFT polymerization by a conjugated organic polymer photocatatyst under red LED irradiation

Hongjie Yang et al.

Summary: This contribution introduces a novel multipath aerobic-mediated reductive quenching pathway for a photoinduced electron transfer reversible addition fragmentation chain transfer polymerization process, achieving the in situ production of a superoxide anion radical from molecular oxygen under red light-emitting diode irradiation in the presence of a conjugated TCPP-DMTA-COP organic polymer.

POLYMER CHEMISTRY (2021)

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Review Chemistry, Multidisciplinary

Branched and Dendritic Polymer Architectures: Functional Nanomaterials for Therapeutic Delivery

Alexander B. Cook et al.

ADVANCED FUNCTIONAL MATERIALS (2020)

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Surface-initiated PET-RAFT polymerization under metal-free and ambient conditions using enzyme degassing

Soyoung E. Seo et al.

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High-Throughput Process for the Discovery of Antimicrobial Polymers and Their Upscaled Production via Flow Polymerization

Peter R. Judzewitsch et al.

MACROMOLECULES (2020)

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Efficient Photoinitiated Polymerization-Induced Self-Assembly with Oxygen Tolerance through Dual-Wavelength Type I Photoinitiation and Photoinduced Deoxygenation

Dongdong Liu et al.

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pH and thermal dual-responsive poly(NIPAM-co-GMA)-coated magnetic nanoparticles via surface-initiated RAFT polymerization for controlled drug delivery

Ali Pourjavadi et al.

MATERIALS SCIENCE AND ENGINEERING C-MATERIALS FOR BIOLOGICAL APPLICATIONS (2020)

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Polymerizations in Continuous Flow: Recent Advances in the Synthesis of Diverse Polymeric Materials

Marcus H. Reis et al.

ACS MACRO LETTERS (2020)

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Semiconductor Quantum Dots Are Efficient and Recyclable Photocatalysts for Aqueous PET-RAFT Polymerization

Kevin P. McClelland et al.

ACS MACRO LETTERS (2020)

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Antifouling Polymer Brushes via Oxygen-Tolerant Surface-Initiated PET-RAFT

Andriy R. Kuzmyn et al.

LANGMUIR (2020)

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Yucheng Zhao et al.

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Benchtop Preparation of Polymer Brushes by SI-PET-RAFT: The Effect of the Polymer Composition and Structure on Inhibition of a Pseudomonas Biofilm

Gervase Ng et al.

ACS APPLIED MATERIALS & INTERFACES (2020)

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Functionalized graphene oxide as a vehicle for targeted drug delivery and bioimaging applications

Neha Karki et al.

JOURNAL OF MATERIALS CHEMISTRY B (2020)

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3D printing and growth induced bending based on PET-RAFT polymerization

Chris William Anderson Bainbridge et al.

POLYMER CHEMISTRY (2020)

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Polymerization techniques in polymerization-induced self-assembly (PISA)

Chao Liu et al.

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Oxygen Tolerant PET-RAFT Facilitated 3D Printing of Polymeric Materials under Visible LEDs

Ali Bagheri et al.

ACS APPLIED POLYMER MATERIALS (2020)

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Nitroxide-Mediated Polymerization: A Versatile Tool for the Engineering of Next Generation Materials

Halynne R. Lamontagne et al.

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Rapid Oxygen Tolerant Aqueous RAFT Photopolymerization in Continuous Flow Reactors

Neomy Zaquen et al.

MACROMOLECULES (2019)

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SI-PET-RAFT: Surface-Initiated Photoinduced Electron Transfer-Reversible Addition-Fragmentation Chain Transfer Polymerization

Mingxiao Li et al.

ACS MACRO LETTERS (2019)

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Far-Red Light-Induced Reversible Addition-Fragmentation Chain Transfer Polymerization Using a Man-Made Bacteriochlorin

Hongliang Cao et al.

ACS MACRO LETTERS (2019)

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Engineering of Molecular Geometry in Bottlebrush Polymers

Dylan J. Walsh et al.

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Enhancement of the growth of polymer brushes via ATRP initiated from ions-releasing indium tin oxide substrates

Anna Gruszkiewicz et al.

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Versatile PISA templates for tailored synthesis of nanoparticles

Yaoming Zhang et al.

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Continuous Flow Fabrication of Block Copolymer-Grafted Silica Micro-Particles in Environmentally Friendly Water/Ethanol Media

Piaoran Ye et al.

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Guiding the Design of Organic Photocatalyst for PET-RAFT Polymerization: Halogenated Xanthene Dyes

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Application of oxygen tolerant PET-RAFT to polymerization-induced self-assembly

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Nathaniel Corrigan et al.

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Yuji Higaki et al.

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Tugba Bilgic et al.

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Exploiting Metalloporphyrins for Selective Living Radical Polymerization Tunable over Visible Wavelengths

Sivaprakash Shanmugam et al.

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Organo-photocatalysts for photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization

Jiangtao Xu et al.

POLYMER CHEMISTRY (2015)

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Strategies to Reduce Oxygen Inhibition in Photoinduced Polymerization

Samuel Clark Ligon et al.

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A guide to the synthesis of block copolymers using reversible-addition fragmentation chain transfer (RAFT) polymerization

Daniel J. Keddie

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A Robust and Versatile Photoinduced Living Polymerization of Conjugated and Unconjugated Monomers and Its Oxygen Tolerance

Jiangtao Xu et al.

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Photoinduced Electron Transfer-Reversible Addition-Fragmentation Chain Transfer (PET-RAFT) Polymerization of Vinyl Acetate and N-Vinylpyrrolidinone: Kinetic and Oxygen Tolerance Study

Sivaprakash Shanmugam et al.

MACROMOLECULES (2014)

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Oxygen Tolerance Study of Photoinduced Electron Transfer-Reversible Addition-Fragmentation Chain Transfer (PET-RAFT) Polymerization Mediated by Ru(bpy)3Cl2

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