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

---

Customizable and Reconfigurable Surface Properties of Printed Micro‐objects by 3D Direct Laser Writing via Nitroxide Mediated Photopolymerization

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(39)

Published: Jan. 12, 2023

Abstract Photoactivated Reversible Deactivation Radical Polymerization (RDRP) technologies have emerged very recently in the field of 3D printing systems especially at macroscale vat‐photopolymerization‐based processes such as digital light processing (DLP). Contrary to conventional free radical photopolymerization, photoRDRP leads objects with living character and thus confers them unique ability be post‐modified after fabrication. While direct laser writing (3D DLW) by two photon polymerization has become a standard for fabrication complex micro‐objects, use RDRP its associated benefits so far been under‐investigated that scale. Herein, photoresist suitable DLW based on nitroxide mediated photopolymerization (NMP2) is developed. The efficiency micro‐structures their subsequent post‐modification are investigated regarding power wavelength excitation. Moreover, highly tunable, precise, successive surface patterning 2D multi‐material microstructures demonstrated thanks spatial temporal control offered photo‐induced post‐modification. This work highlights new directions explored order accelerate adoption photopolymerization.

Language: Английский

---

Application of RAFT in 3D Printing: Where Are the Future Opportunities?

Macromolecules, Journal Year: 2023, Volume and Issue: 56(5), P. 1778 - 1797

Published: March 3, 2023

Research into 3D printing using reversible addition–fragmentation chain transfer (RAFT) polymerization has garnered interest since it was first reported in 2019. This technique initially developed to expand the scope of light-based technologies by producing materials that can be modified postprinting, termed "living" printing. The livingness achieved incorporating reactivatable RAFT functionalities within polymer networks, enabling after As field RAFT-mediated progressed, further studies have revealed its applications advanced materials. These include spatially resolved surface functionalization and patterning, self-healing, welding, nano- microscale structuring polymers. Additionally, enables production scaffolds with controlled interconnected channel-pore architecture, suitable for customized drug delivery. Perspective provides a review chemical mechanisms employed highlights manufactured through this technology. Potential research directions are also discussed organized future investigation.

Language: Английский

---

Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C–H Functionalization

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(17), P. 10192 - 10280

Published: Aug. 8, 2024

Radical C–H functionalization represents a useful means of streamlining synthetic routes by avoiding substrate preactivation and allowing access to target molecules in fewer steps. The first-row transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu) are Earth-abundant can be employed regulate radical functionalization. use such is desirable because the diverse interaction modes between metal complexes species including addition center, ligand complexes, substitution single-electron transfer radicals hydrogen atom noncovalent complexes. Such interactions could improve reactivity, diversity, selectivity transformations allow for more challenging reactions. This review examines achievements this promising area over past decade, with focus on state-of-the-art while also discussing existing limitations enormous potential high-value regulated these metals. aim provide reader detailed account strategies mechanisms associated

Language: Английский

---

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

---

Fully Degradable Polyacrylate Networks from Conventional Radical Polymerization Enabled by Thionolactone Addition

Macromolecules, Journal Year: 2022, Volume and Issue: 55(15), P. 6695 - 6702

Published: July 25, 2022

We report the preparation of degradable polymer networks by conventional free radical copolymerization n-butyl acrylate with a crosslinker (1 mol %) and dibenzo[c,e]oxepane-5-thione (DOT) as strand-cleaving comonomer. Addition only 4 % DOT imparts synthesized full degradability aminolysis, whereas gels less (2–3 cannot be degraded. This data confirms recently proposed reverse gel-point model for prepared polymerization demonstrates importance considering kinetics when designing fully gels. Notably, even though significantly slows down delays gelation, it has minimal effect on physical properties such shear storage modulus, equilibrium swelling ratio, glass transition temperature, or thermal stability.

Language: Английский

---

Wavelength-Resolved PhotoATRP

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(3), P. 1094 - 1098

Published: Jan. 10, 2022

The careful mapping of photoinduced reversible-deactivation radical polymerizations (RDRP) is a prerequisite for their applications in soft matter materials design. Here, we probe the wavelength-dependent behavior photochemically induced atom transfer polymerization (ATRP) using nanosecond pulsed-laser (PLP). photochemical reactivities at identical photon fluxes methyl acrylate terms conversion, number-average molecular weight, and dispersity resulting polymers are mapped against absorption spectrum copper(II) catalyst range 305–550 nm. We observe red shift action relative to catalyst. Both weight show wavelength dependence, while conversion remain linearly correlated. reported data allow judicious selection optimum wavelengths photoATRP.

Language: Английский

---

Fast Living 3D Printing via Free Radical Promoted Cationic RAFT Polymerization

Small, Journal Year: 2023, Volume and Issue: 19(50)

Published: Jan. 27, 2023

The application of reversible deactivation radical polymerization techniques in 3D printing is emerging as a powerful method to build "living" polymer networks, which can be easily postmodified with various functionalities. However, the building speed these systems still limited compared commercial systems. Herein, digital light processing (DLP)-based system via photoinduced free radical-promoted cationic addition-fragmentation chain transfer vinyl ethers, objects by DLP printer at relatively fast (12.99 cm h-1 ), reported. behavior and conditions are studied detail. livingness printed demonstrated spatially controlled postmodification fluorescent monomer.

Language: Английский

---

Controlling mechanical properties of 3D printed polymer composites through photoinduced reversible addition–fragmentation chain transfer (RAFT) polymerization

Polymer Chemistry, Journal Year: 2021, Volume and Issue: 13(1), P. 44 - 57

Published: Oct. 13, 2021

Reversible addition–fragmentation chain-transfer (RAFT) polymerization has been exploited to design silica-nanoparticle-incorporated photocurable resins for 3D printing of materials with enhanced mechanical properties and complex structures.

Language: Английский

---

Living polymer networks prepared by controlled radical polymerization techniques

Polymer Chemistry, Journal Year: 2022, Volume and Issue: 13(11), P. 1484 - 1494

Published: Jan. 1, 2022

Much has been done towards the traditional usage of controlled radical polymerization, but with a far lesser degree work in polymer networks. Here, we cover both parent and daughter networks, finish by looking at their future potential.

Language: Английский

---