Red-Light-Driven Atom Transfer Radical Polymerization for High-Throughput Polymer Synthesis in Open Air

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

---

Photocatalytic ATRP Depolymerization: Temporal Control at Low ppm of Catalyst Concentration

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(39), P. 21146 - 21151

Published: Sept. 22, 2023

A photocatalytic ATRP depolymerization is introduced that significantly suppresses the reaction temperature from 170 to 100 °C while enabling temporal regulation. In presence of low-toxicity iron-based catalysts and under visible light irradiation, near-quantitative monomer recovery could be achieved (up 90%), albeit with minimal control. By employing ppm concentrations either FeCl2 or FeCl3, during dark periods completely eliminated, thus control possibility modulate rate by simply turning "on" "off". Notably, our approach allowed preservation end-group fidelity throughout reaction, carried out at high polymer loadings 2M), was compatible various polymers sources. This methodology provides a facile, environmentally friendly, temporally regulated route chemically recycle ATRP-synthesized polymers, opening door for further opportunities.

Language: Английский

---

Emerging trends in development and application of 3D printed nanocomposite polymers for sustainable environmental solutions

European Polymer Journal, Journal Year: 2023, Volume and Issue: 196, P. 112298 - 112298

Published: July 13, 2023

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

---

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

---

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

---

Design and 3D Printing of Polyacrylonitrile‐Derived Nanostructured Carbon Architectures

Small Science, Journal Year: 2024, Volume and Issue: 4(4)

Published: Feb. 27, 2024

Nanostructured carbon materials with designer geometries are of great interest for a wide range energy‐based and environmental applications due to their tunable microstructure, which allows optimized properties performance, as well ability be shaped in complex three‐dimensional (3D) suited targeted applications. However, achieving controllable way preparing nanostructured precise macroscale control has proven challenging. Herein, straightforward approach 3D printing polyacrylonitrile (PAN)‐derived controlled by employing self‐assembling resins liquid crystal display is presented. The correlation between resin composition, parameters, PAN thermal transformation conditions identified using combination thermoanalytical structural techniques. readily transformed into voided microstructure while retaining the original macro‐architecture printed polymer precursor objects. resulting electrically conductive feature nitrogen active sites pyrolysis temperature. This method offers simple produce carbon‐based an arbitrary shape, presenting possibility advantageous characteristics potential both fields energy environment.

Language: Английский

---

Recent advances in implantable sensors and electronics using printable materials for advanced healthcare

Biosensors and Bioelectronics, Journal Year: 2024, Volume and Issue: 257, P. 116302 - 116302

Published: April 17, 2024

Language: Английский

---

Microphase Separation 3D Printing of Binary Inorganic Polymer Precursors to Prepare Nanostructured Carbon‐Ceramic Multimaterials

Advanced Materials Technologies, Journal Year: 2024, Volume and Issue: 9(13)

Published: April 18, 2024

Abstract Traditionally, combining carbon and ceramic materials has been challenging due to their different chemical physical properties. Despite the development of numerous methodologies for synthesis, these techniques frequently necessitate intricate, multi‐stage protocols specialized equipment. This study introduces a novel approach fabricating nanostructured carbon‐ceramic multimaterials through polymerization‐induced microphase separation 3D printing. By inorganic precursors, polycarbosilane, acrylonitrile (AN) within photocurable resin, heterogeneous composed PAN‐preceramic sacrificial polymer phases are printed. Upon pyrolysis, domains transformed into matrix while thermally decomposed yield nanoscale voids. The utilization synchrotron X‐ray spectroscopy microscopy revealed that phase compositions microstructure resulting multi‐materials significantly influenced by initial composition resins. co‐existence single printed material brought together combination properties from both phases, such as low thermal conductivity ceramics relatively high electrical carbon, along with exceptional resistance. insights microstructure, atomic configuration, property relationships have broad implications multi‐phase hybrid materials.

Language: Английский

---

Xolography for the Production of Polymeric Multimaterials

Advanced Materials Technologies, Journal Year: 2024, Volume and Issue: 9(15)

Published: April 1, 2024

Abstract Three‐dimensional (3D) printed multimaterials have quickly grown in interest as researchers aim to mimic the material chemistry and geometric complexity of natural materials. While some exceptional multimaterial 3D printing systems been developed, there is still a shortfall scope production these More recently, introduction xolography single‐step, auxiliary‐free additive manufacturing approach has enabled rapid materials with geometries inaccessible via other techniques. However, previous required resins high transparency for effective formation, formation not demonstrated. In this work, reversible deactivation radical polymerization used resin composition, viscosity, processing parameters are explored develop new capable application visible light‐mediated xolography. After optimization, non‐transparent containing thiocarbonylthio species applied manufacture geometrically complex, The resulting polymer network can be functionalized embedded moieties impart functionality Finally, unique capabilities demonstrated featuring chemically disparate domains 3D‐spatial control. This two‐step overprinting operationally simple provides avenue polymeric printing.

Language: Английский

---