Sustainable Chemistry and Pharmacy, Journal Year: 2025, Volume and Issue: 45, P. 101988 - 101988
Published: March 14, 2025
Language: Английский
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
Citations
58
European Polymer Journal, Journal Year: 2024, Volume and Issue: 211, P. 113001 - 113001
Published: March 30, 2024
Atom transfer radical polymerization (ATRP) is one of the most often used controlled techniques. It employs very small amounts (ppm) Cu complexes in presence various chemical reducing agents but also external stimuli such as light, electrical current or mechanical forces. can be carried out bulk, solution, and dispersed media. ATRP has been successfully to prepare polymers with architecture well-defined topology, composition, functionality, well bioconjugates organic–inorganic hybrids. This article summarizes status an outlook for ATRP.
Language: Английский
Citations
23
Macromolecules, Journal Year: 2023, Volume and Issue: 56(5), P. 2017 - 2026
Published: Feb. 20, 2023
Over the last decade, photoinduced ATRP techniques have been developed to harness energy of light generate radicals. Most these methods require use UV initiate polymerization. However, has several disadvantages: it can degrade proteins, damage DNA, cause undesirable side reactions, and low penetration depth in reaction media. Recently, we demonstrated green-light-induced with dual catalysis, where eosin Y (EYH2) was used as an organic photoredox catalyst conjunction a copper complex. This catalysis proved be highly efficient, allowing rapid well-controlled aqueous polymerization oligo(ethylene oxide) methyl ether methacrylate without need for deoxygenation. Herein, expanded this system synthesize polyacrylates under biologically relevant conditions using CuII/Me6TREN (Me6TREN = tris[2-(dimethylamino)ethyl]amine) EYH2 at ppm levels. Water-soluble acrylate (average Mn 480, OEOA480) polymerized open vessels green irradiation (520 nm). Despite continuous oxygen diffusion, high monomer conversions were achieved within 40 min, yielding polymers narrow molecular weight distributions (1.17 ≤ D̵ 1.23) wide targeted DP range (50–800). In situ chain extension block copolymerization confirmed preserved end functionality. addition, triggered/halted by turning on/off light, showing temporal control. The optimized also enabled controlled various hydrophilic monomers, such 2-hydroxyethyl acrylate, 2-(methylsulfinyl)ethyl acrylate), zwitterionic carboxy betaine acrylate. Notably, method allowed synthesis well-defined acrylate-based protein-polymer hybrids straightforward setup rigorous
Language: Английский
Citations
39
ACS Macro Letters, Journal Year: 2024, Volume and Issue: 13(4), P. 461 - 467
Published: April 4, 2024
Protein–polymer conjugates combine the unique properties of both proteins and synthetic polymers, making them important materials for biomedical applications. In this work, we synthesized characterized protein-branched polymer bioconjugates that were precisely designed to retain protein functionality while preventing unwanted interactions. Using chymotrypsin as a model protein, employed controlled radical branching polymerization (CRBP) technique utilizing water-soluble inibramer, sodium 2-bromoacrylate. The green-light-induced atom transfer (ATRP) enabled grafting branched polymers directly from surface in open air. resulting exhibited predetermined molecular weight, well-defined architecture, high density. Conformational analysis by SEC-MALS validated polymers. Furthermore, enzymatic assays revealed densely grafted prevented inhibitor penetration, retained up 90% their activity. This study demonstrates promising strategy designing protein–polymer with tunable sieving behavior, opening avenues applications drug delivery biotechnology.
Language: Английский
Citations
13
Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)
Published: June 17, 2024
Abstract Atom transfer radical polymerization (ATRP) with dual photoredox/copper catalysis combines the advantages of photo-ATRP and photoredox-mediated ATRP, utilizing visible light ensuring broad monomer scope solvent compatibility while minimizing side reactions. Despite its popularity, challenges include high photocatalyst (PC) loadings (10 to 1000 ppm), requiring additional purification increasing costs. In this study, we discover a PC that functions at sub-ppm level for ATRP through mechanism-driven design. Through studying mechanisms, find efficient polymerizations are driven by PCs whose ground state oxidation potential—responsible regeneration—play more important role than their excited reducing power, responsible initiation. This is verified screening varying redox potentials triplet generation capabilities. Based on these findings, identify highly PC, 4DCDP-IPN, featuring moderate power maximized potential. Employing 50 ppb, synthesize poly(methyl methacrylate) conversion, narrow molecular weight distribution, chain-end fidelity. system exhibits oxygen tolerance supports large-scale reactions under ambient conditions. Our systematic design, offer meaningful insights controlled metallaphotoredox-mediated syntheses beyond ATRP.
Language: Английский
Citations
13
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 9112 - 9123
Published: March 19, 2024
Recent advances have demonstrated the promise of complex multicomponent polymeric supports to enable supra-biological enzyme performance. However, discovery such has been limited by time-consuming, low-throughput synthesis and screening. Here, we describe a novel combinatorial high-throughput platform that enables rapid screening heterogeneous copolymer brushes as immobilization supports, named support (CHESS). Using 384-well plate format, synthesized arrays three-component polymer in microwells using photoactivated surface-initiated polymerization immobilized enzymes situ. The utility CHESS identify optimal under thermally chemically denaturing conditions was usingBacillus subtilisLipase A (LipA). identification with compositions validated immobilizing LipA on polymer-brush-modified biocatalyst particles. We further could be used predict composition priori for previously unexplored enzyme, alkaline phosphatase (AlkP). Our findings demonstrate represents predictable reliable dramatically accelerating search chemical facilitates biocompatible stabilizing materials.
Language: Английский
Citations
10
Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(26), P. 14435 - 14445
Published: June 26, 2023
Combining synthetic polymers with RNA paves the way for creating RNA-based materials non-canonical functions. We have developed an acylation reagent that allows direct incorporation of atom transfer radical polymerization (ATRP) initiator into both short oligoribonucleotides and natural biomass extracted from torula yeast. The was performed in a quantitative yield. resulting initiator-functionalized RNAs were used grafting polymer chains by photoinduced ATRP, RNA-polymer hybrids narrow molecular weight distributions. oligo(ethylene oxide) methyl ether methacrylate, poly(ethylene glycol) dimethacrylate, N-isopropylacrylamide monomers, bottlebrushes, hydrogels, stimuli-responsive materials. This approach, readily applicable to post-synthetic nature-derived RNA, can be engineer properties variety macromolecular assemblies providing access wide hybrids.
Language: Английский
Citations
22
Macromolecules, Journal Year: 2023, Volume and Issue: 57(3), P. 830 - 846
Published: Dec. 1, 2023
Branched polymers have aroused great interest due to their less chain entanglement, high concentration of terminals, good solubility, and low viscosity in melts solutions. In this Perspective, we highlight various synthesis strategies for branched with different structures discuss applications the field solid polymer electrolytes lithium batteries, coatings membranes, surfactants, hydrogels, so on. Here, expect arouse more approaches such as enzyme-catalyzed living radical polymerization photoinitiated also copolymerize monomers properties or modify order obtain functionalized that can be produced under mild conditions.
Language: Английский
Citations
19
Chemical Science, Journal Year: 2024, Volume and Issue: 15(25), P. 9742 - 9755
Published: Jan. 1, 2024
A photoinduced reversible addition-fragmentation chain-transfer (photo-RAFT) polymerization technique in the presence of sodium pyruvate (SP) and pyruvic acid derivatives was developed.
Language: Английский
Citations
8
Macromolecules, Journal Year: 2024, Volume and Issue: 57(11), P. 5368 - 5379
Published: May 29, 2024
Topology significantly impacts polymer properties and applications. Hyperbranched polymers (HBPs) synthesized via atom transfer radical polymerization (ATRP) using inimers typically exhibit broad molecular weight distributions limited control over branching. Alternatively, copolymerization of inibramers (IB), such as α-chloro/bromo acrylates with vinyl monomers, yields HBPs precise uniform Herein, we described the synthesis hydrophilic HB polyacrylates in water by copolymerizing a water-soluble IB, oligo(ethylene oxide) methyl ether 2-bromoacrylate (OEOBA), various acrylate comonomers. Visible-light-mediated controlled branching (CRBP) dual catalysis eosin Y (EY) copper complexes resulted weights (Mn = 38 000 to 170 000) degrees (2%–24%). Furthermore, optimized conditions enabled successful application OEOBA synthesize linear-hyperbranched block copolymers hyperbranched protein hybrids (HB-PPH), demonstrating its potential advance complex macromolecular architecture under environmentally benign conditions. Copolymerization methacrylate monomer, (OEOMA500), inibramer was accompanied fragmentation β-carbon C–C bond scission subsequent growth chains from fragments. computational studies investigating depending on IB comonomer structure supported experimental observations. This work expands toolkit for CRBP highlights critical influence reaction outcomes.
Language: Английский
Citations
7