Robust Miniemulsion PhotoATRP Driven by Red and Near-Infrared Light.

Photoinduced polymerization techniques have gathered significant attention due to their mild conditions, spatiotemporal control, and simple setup. In addition to homogeneous media, efforts have been made to implement photopolymerization in emulsions as a practical and greener process. However, previous photoinduced reversible deactivation radical polymerization (RDRP) in heterogeneous media has relied on short-wavelength lights, which have limited penetration depth, resulting in slow polymerization and relatively poor control. In this study, we demonstrate the first example of a highly efficient photoinduced miniemulsion ATRP in the open air driven by red or near-infrared (NIR) light. This was facilitated by the utilization of a water-soluble photocatalyst, methylene blue (MB+). Irradiation by red/NIR light allowed for efficient excitation of MB+ and subsequent photoreduction of the ATRP deactivator in the presence of water-soluble electron donors to initiate and mediate the polymerization process. The NIR light-driven miniemulsion photoATRP provided a successful synthesis of polymers with low dispersity (1.09 ≤ D ≤ 1.29) and quantitative conversion within an hour. This study further explored the impact of light penetration on polymerization kinetics in reactors of varying sizes and a large-scale reaction (250 mL), highlighting the advantages of longer-wavelength light, particularly NIR light, for large-scale polymerization in dispersed media owing to its superior penetration. This work opens new avenues for robust emulsion photopolymerization techniques, offering a greener and more practical approach with improved control and efficiency.

Nucleic Acid-Binding Dyes as Versatile Photocatalysts for Atom-Transfer Radical Polymerization.

Nucleic acid-binding dyes (NuABDs) are fluorogenic probes that light up after binding to nucleic acids. Taking advantage of their fluorogenicity, NuABDs have been widely utilized in the fields of nanotechnology and biotechnology for diagnostic and analytical applications. We demonstrate the potential of NuABDs together with an appropriate nucleic acid scaffold as an intriguing photocatalyst for precisely controlled atom-transfer radical polymerization (ATRP). Additionally, we systematically investigated the thermodynamic and electrochemical properties of the dyes, providing insights into the mechanism that drives the photopolymerization. The versatility of the NuABD-based platform was also demonstrated through successful polymerizations using several NuABDs in conjunction with diverse nucleic acid scaffolds, such as G-quadruplex DNA or DNA nanoflowers. This study not only extends the horizons of controlled photopolymerization but also broadens opportunities for nucleic acid-based materials and technologies, including nucleic acid-polymer biohybrids and stimuli-responsive ATRP platforms.

Selective and Controlled Grafting from PVDF-Based Materials by Oxygen-Tolerant Green-Light-Mediated ATRP.

Poly(vinylidene fluoride) (PVDF) shows excellent chemical and thermal resistance and displays high dielectric strength and unique piezoelectricity, which are enabling for applications in membranes, electric insulators, sensors, or power generators. However, its low polarity and lack of functional groups limit wider applications. While inert, PVDF has been modified by grafting polymer chains by atom transfer radical polymerization (ATRP), albeit via an unclear mechanism, given the strong C-F bonds. Herein, we applied eosin Y and green-light-mediated ATRP to modify PVDF-based materials. The method gave nearly quantitative (meth)acrylate monomer conversions within 2 h without deoxygenation and without the formation of unattached homopolymers, as confirmed by control experiments and DOSY NMR measurements. The gamma distribution model that accounts for broadly dispersed polymers in DOSY experiments was essential and serves as a powerful tool for the analysis of PVDF. The NMR analysis of poly(methyl acrylate) graft chain-ends on PVDF-CTFE (statistical copolymer with chlorotrifluoroethylene) was carried out successfully for the first time and showed up to 23 grafts per PVDF-CTFE chain. The grafting density was tunable depending on the solvent composition and light intensity during the grafting. The initiation proceeded either from the C-Cl sites of PVDF-CTFE or via unsaturations in the PVDF backbones. The dehydrofluorinated PVDF was 20 times more active than saturated PVDF during the grafting. The method was successfully applied to modify PVDF, PVDF-HFP, and Viton A401C. The obtained PVDF-CTFE-g-PnBMA materials were investigated in more detail. They featured slightly lower crystallinity than PVDF-CTFE (12-18 vs 24.3%) and had greatly improved mechanical performance: Young's moduli of up to 488 MPa, ductility of 316%, and toughness of 46 × 106 J/m3.

Electrochemically Mediated Atom Transfer Radical Polymerization Driven by Alternating Current.

Alternating current (AC) and pulsed electrolysis are gaining traction in electro(organic) synthesis due to their advantageous characteristics. We employed AC electrolysis in electrochemically mediated Atom Transfer Radical Polymerization (eATRP) to facilitate the regeneration of the activator CuI complex on Cu0 electrodes. Additionally, Cu0 served as a slow supplemental activator and reducing agent (SARA ATRP), enabling the activation of alkyl halides and the regeneration of the CuI activator through a comproportionation reaction. We harnessed the distinct properties of Cu0 dual regeneration, both chemical and electrochemical, by employing sinusoidal, triangular, and square-wave AC electrolysis alongside some of the most active ATRP catalysts available. Compared to linear waveform (DC electrolysis) or SARA ATRP (without electrolysis), pulsed and AC electrolysis facilitated slightly faster and more controlled polymerizations of acrylates. The same AC electrolysis conditions could successfully polymerize eleven different monomers across different mediums, from water to bulk. Moreover, it proved effective across a spectrum of catalyst activity, from low-activity Cu/2,2-bipyridine to highly active Cu complexes with substituted tripodal amine ligands. Chain extension experiments confirmed the high chain-end fidelity of the produced polymers, yielding functional and high molecular-weight block copolymers. SEM analysis indicated the robustness of the Cu0 electrodes, sustaining at least 15 consecutive polymerizations.

Tailored Branched Polymer-Protein Bioconjugates for Tunable Sieving Performance.

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 and characterized protein-branched polymer bioconjugates that were precisely designed to retain protein functionality while preventing unwanted interactions. Using chymotrypsin as a model protein, we employed a controlled radical branching polymerization (CRBP) technique utilizing a water-soluble inibramer, sodium 2-bromoacrylate. The green-light-induced atom transfer radical polymerization (ATRP) enabled the grafting of branched polymers directly from the protein surface in the open air. The resulting bioconjugates exhibited a predetermined molecular weight, well-defined architecture, and high branching density. Conformational analysis by SEC-MALS validated the controlled grafting of branched polymers. Furthermore, enzymatic assays revealed that densely grafted polymers prevented protein inhibitor penetration, and the resulting conjugates retained up to 90% of their enzymatic activity. This study demonstrates a promising strategy for designing protein-polymer bioconjugates with tunable sieving behavior, opening avenues for applications in drug delivery and biotechnology.

Controlled Polymer Synthesis Toward Green Chemistry: Deep Insights into Atom Transfer Radical Polymerization in Biobased Substitutes for Polar Aprotic Solvents.

Cyrene (dihydrolevoglucosenone) and its derivative Cygnet 0.0, recognized as eco-friendly alternatives to polar aprotic solvents, were utilized in atom transfer radical polymerization (ATRP) of a wide range of both hydrophobic and hydrophilic (meth)acrylates. The detailed kinetics study and electrochemical experiments of the catalytic complex in these solvents reveal the opportunities and limitations of their use in controlled radical polymerization. Both solvents produce precisely controlled polymers using supplemental activator and reducing agent (SARA) ATRP. They offer an efficient reaction medium for crafting well-defined branched architectures from naturally derived cores such as riboflavin, ß-cyclodextrin, and troxerutin, thereby significantly expanding the application scope of these solvents. Notably, Cygnet 0.0 significantly reduces side reactions between the solvent and the catalyst compared to Cyrene, allowing the catalyst complex to be used at a reduced concentration down to 75 ppm. The effective mass yield values achieved in Cyrene and Cygnet 0.0 underscore a substantial advantage of these solvents over DMF in generating processes that adhere to the principles of green chemistry. Furthermore, the copper residue in the final polymers was several hundred times lower than the permissible daily exposure to orally administered copper in pharmaceuticals. As a result, the resulting polymeric materials hold immense potential for various applications, including the pharmaceutical industry.

Synthesis of Mechanically Robust Very High Molecular Weight Polyisoprene Particle Brushes by Atom Transfer Radical Polymerization.

Linear polyisoprene (PI) and SiO2-g-PI particle brushes were synthesized by both conventional and activators regenerated by electron transfer (ARGET) atom transfer radical polymerization (ATRP). The morphology and solution state study on the particle brushes by transmission electron microscopy (TEM) and dynamic light scattering (DLS) confirmed the successful grafting of PI ligands on the silica surface. The presence of nanoparticle clusters suggests low grafting density (associated with the limited initiation efficiency of ARGET for PI). Nevertheless, particle brushes with very high molecular weights, Mn > 300,000, were prepared, which significantly improved the dispersion of silica nanoparticles and also contributed to excellent mechanical performance. The reinforcing effects of SiO2 nanofillers and very high molecular weight PI ligands were investigated by dynamic mechanical analysis (DMA) as well as computational simulation for the cured linear PI homopolymer/SiO2-g-PI particle brush bulk films.

Bioinspired Bottlebrush Polymers Effectively Alleviate Frictional Damage Both In Vitro and In Vivo.

Bottlebrush polymers (BB) have emerged as compelling candidates for biosystems to face tribological challenges, including friction and wear. This study provides a comprehensive assessment of an engineered triblock BB polymer's affinity, cell toxicity, lubrication, and wear protection in both in vitro and in vivo settings, focusing on applications for conditions like osteoarthritis and dry eye syndrome. Results show that the designed polymer rapidly adheres to various surfaces (e.g., cartilage, eye, and contact lens), forming a robust, biocompatible layer for surface lubrication and protection. The tribological performance and biocompatibility are further enhanced in the presence of hyaluronic acid (HA) both in vitro and in vivo. The exceptional lubrication performance and favorable interaction with HA position the synthesized triblock polymer as a promising candidate for innovative treatments addressing deficiencies in bio-lubricant systems.

Copper Nanodrugs by Atom Transfer Radical Polymerization.

In this study, some copper catalysts used for atom transfer radical polymerization (ATRP) were explored as efficient anti-tumor agents. The aqueous solution of copper-containing nanoparticles with uniform spheric morphology was in situ prepared through a copper-catalyzed activator generated by electron transfer (AGET) ATRP in water. Nanoparticles were then directly injected into tumor-bearing mice for antitumor chemotherapy. The copper nanodrugs had prolonged blood circulation time and enhanced accumulation at tumor sites, thus showing potent antitumor activity. This work provides a novel strategy for precise and large-scale preparation of copper nanodrugs with high antitumor activity.

Block Copolymers of Polyolefins with Polyacrylates: Analyzing and Improving the Blocking Efficiencies Using MILRad/ATRP Approach.

Despite their industrial ubiquity, polyolefin-polyacrylate block copolymers are challenging to synthesize due to the distinct polymerization pathways necessary for respective blocks. This study utilizes MILRad, metal-organic insertion light-initiated radical polymerization, to synthesize polyolefin-b-poly(methyl acrylate) copolymer by combining palladium-catalyzed insertion-coordination polymerization and atom transfer radical polymerization (ATRP). Brookhart-type Pd complexes used for the living polymerization of olefins are homolytically cleaved by blue-light irradiation, generating polyolefin-based macroradicals, which are trapped with functional nitroxide derivatives forming ATRP macroinitiators. ATRP in the presence of Cu(0), that is, supplemental activators and reducing agents , is used to polymerize methyl acrylate. An increase in the functionalization efficiency of up to 71% is demonstrated in this study by modifying the light source and optimizing the radical trapping condition. Regardless of the radical trapping efficiency, essentially quantitative chain extension of polyolefin-Br macroinitiator with acrylates is consistently demonstrated, indicating successful second block formation.

The Importance of Bulk Viscoelastic Properties in "Self-Healing" of Acrylate-Based Copolymer Materials.

"Self-healing" has emerged as a concept to increase the functional stability and durability of polymer materials in applications and thus to benefit the sustainability of polymer-based technologies. Recently, van der Waals (vdW)-driven "self-healing" of sequence-controlled acrylate-based copolymers due to "key-and-lock"- or "ring-and-lock"-type interactions has generated considerable interest as a viable route toward engineering polymers with "self-healing" ability. This contribution systematically evaluates the time, temperature, and composition dependence of the mechanical recovery of acrylate-based copolymer and homopolymer systems subject to cut-and-adhere testing. "Self-healing" in n-butyl acrylate/methyl methacrylate (BA/MMA)- or n-butyl acrylate/styrene (BA/Sty)-based copolymers with varying composition and sequence is found to correlate with the bulk viscoelastic properties of materials and to follow a similar trend as other tested acrylate-based homo- and copolymers. This suggests that "self-healing" in this class of materials is more related to the chain dynamics of bulk materials rather than composition- or sequence-dependent specific interactions.

Architecture Controls Phonon Propagation in All-Solid Brush Colloid Metamaterials.

Brillouin light scattering and elastodynamic theory are concurrently used to determine and interpret the hypersonic phonon dispersion relations in brush particle solids as a function of the grafting density with perspectives in optomechanics, heat management, and materials metrology. In the limit of sparse grafting density, the phonon dispersion relations bear similarity to polymer-embedded colloidal assembly structures in which phonon dispersion can be rationalized on the basis of perfect boundary conditions, i.e., isotropic stiffness transitions across the particle interface. In contrast, for dense brush assemblies, more complex dispersion characteristics are observed that imply anisotropic stiffness transition across the particle/polymer interface. This provides direct experimental validation of phonon propagation changes associated with chain conformational transitions in dense particle brush materials. A scaling relation between interface tangential stiffness and crowding of polymer tethers is derived that provides a guideline for chemists to design brush particle materials with tailored phononic dispersion characteristics. The results emphasize the role of interfaces in composite materials systems. Given the fundamental relevance of phonon dispersion to material properties such as thermal transport or mechanical properties, it is also envisioned that the results will spur the development of novel functional hybrid materials.

Light-Mediated Polymerization Catalyzed by Carbon Nanomaterials.

Carbon nanomaterials, specifically carbon dots and carbon nitrides, play a crucial role as heterogeneous photoinitiators in both radical and cationic polymerization processes. These recently introduced materials offer promising solutions to the limitations of current homogeneous systems, presenting a novel approach to photopolymerization. This review highlights the preparation and photocatalytic performance of these nanomaterials, emphasizing their application in various polymerization techniques, including photoinduced i) free radical, ii) RAFT, iii) ATRP, and iv) cationic photopolymerization. Additionally, it discusses their potential in addressing contemporary challenges and explores prospects in this field. Moreover, carbon nitrides, in particular, exhibit exceptional oxygen tolerance, underscoring their significance in radical polymerization processes and allowing their applications such as 3D printing, surface modification of coatings, and hydrogel engineering.

Visible-light-induced ATRP under high-pressure: synthesis of ultra-high-molecular-weight polymers.

In this study, a high-pressure-assisted photoinduced atom transfer radical polymerization (p ≤ 250 MPa) enabled the synthesis of ultra-high-molecular-weight polymers (UHMWPs) of up to 9 350 000 and low/moderate dispersity (1.10 < D < 1.46) in a co-solvent system (water/DMSO), without reaction mixture deoxygenation.

Composition-Orientation Induced Mechanical Synergy in Nanoparticle Brushes with Grafted Gradient Copolymers.

Gradient poly(methyl methacrylate/n-butyl acrylate) copolymers, P(MMA/BA), with various compositional ratios, were grafted from surface-modified silica nanoparticles (SiO2-g-PMMA-grad-PBA) via complete conversion surface-initiated activator regenerated by electron transfer (SI-ARGET) atom transfer radical polymerization (ATRP). Miniemulsion as the reaction medium effectively confined the interparticle brush coupling within micellar compartments, preventing macroscopic gelation and enabling complete conversion. Isolation of dispersed and gelled fractions revealed dispersed particle brushes to feature a higher Young's modulus, toughness, and ultimate strain compared with those of the "gel" counterparts. Upon purification, brush nanoparticles from the dispersed phase formed uniform microstructures. Uniaxial tension testing revealed a "mechanical synergy" for copolymers with MMA/BA = 3:2 molar ratio to concurrently exhibit higher toughness and stiffness. When compared with linear analogues of similar composition, the brush nanoparticles with gradient copolymers had better mechanical properties, attributed to the synergistic effects of the combination of composition and propagation orientation, highlighting the significance of architectural design for tethered brush layers of such hybrid materials.

Biomass RNA for the Controlled Synthesis of Degradable Networks by Radical Polymerization.

Nucleic acids extracted from biomass have emerged as sustainable and environmentally friendly building blocks for the fabrication of multifunctional materials. Until recently, the fabrication of biomass nucleic acid-based structures has been facilitated through simple crosslinking of biomass nucleic acids, which limits the possibility of material properties engineering. This study presents an approach to convert biomass RNA into an acrylic crosslinker through acyl imidazole chemistry. The number of acrylic moieties on RNA was engineered by varying the acylation conditions. The resulting RNA crosslinker can undergo radical copolymerization with various acrylic monomers, thereby offering a versatile route for creating materials with tunable properties (e.g., stiffness and hydrophobic characteristics). Further, reversible-deactivation radical polymerization methods, such as atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT), were also explored as additional approaches to engineer the hydrogel properties. The study also demonstrated the metallization of the biomass RNA-based material, thereby offering potential applications in enhancing electrical conductivity. Overall, this research expands the opportunities in biomass-based biomaterial fabrication, which allows tailored properties for diverse applications.

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

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 complex multistep synthesis. Herein, we present the first example of fully oxygen-tolerant red/NIR-light-mediated photoinduced atom transfer radical polymerization (photo-ATRP) in a high-throughput manner under biologically relevant conditions. The method uses commercially available methylene blue (MB+) as the PC and [X-CuII/TPMA]+ (TPMA = tris(2-pyridylmethyl)amine) complex as the deactivator. The mechanistic study revealed that MB+ undergoes a reductive quenching cycle in the presence of the TPMA ligand used in excess. The formed semireduced MB (MB•) sustains polymerization by regenerating the [CuI/TPMA]+ activator and together with [X-CuII/TPMA]+ provides control over the polymerization. This dual catalytic system exhibited excellent oxygen tolerance, enabling polymerizations with high monomer conversions (>90%) in less than 60 min at low volumes (50-250 µL) and high-throughput synthesis of a library of well-defined polymers and DNA-polymer bioconjugates with narrow molecular weight distributions (D < 1.30) in an open-air 96-well plate. In addition, the broad absorption spectrum of MB+ allowed ATRP to be triggered under UV to NIR irradiation (395-730 nm). This opens avenues for the integration of orthogonal photoinduced reactions. Finally, the MB+/Cu catalysis showed good biocompatibility during polymerization in the presence of cells, which expands the potential applications of this method.

Tailored PVDF Graft Copolymers via ATRP as High-Performance NCM811 Cathode Binders.

High-nickel layered oxides, e.g., LiNi0.8Co0.1Mn0.1O2 (NCM811), are promising candidates for cathode materials in high-energy-density lithium-ion batteries (LIBs). Complementing the notable developments of modification of active materials, this study focused on the polymer binder materials, and a new synthetic route was developed to engineer PVDF binders by covalently grafting copolymers from poly(vinylidene fluoride-co-chlorotrifluoroethylene) (PVDF-CTFE) with multiple functionalities using atom transfer radical polymerization (ATRP). The grafted random copolymer binder provided excellent flexibility (319% elongation), adhesion strength (50 times higher than PVDF), transition metal chelation capability, and efficient ionic conductivity pathways. The NCM811 half-cells using the designed binders exhibited a remarkable rate capability of 143.4 mA h g-1 at 4C and cycling stability with 70.1% capacity retention after 230 cycles at 0.5 C, which is much higher than the 52.3% capacity retention of nonmodified PVDF. The well-retained structure of NCM811 with the designed binder was systematically studied and confirmed by post-mortem analysis.

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

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

Copolymer Brush Particle Hybrid Materials with "Recall-and-Repair" Capability.

The effect of sequence structure on the self-healing and shape-memory properties of copolymer-tethered brush particle films was investigated and compared to linear copolymer analogs. Poly(n-butyl acrylate-co-methyl methacrylate), P(BA-co-MMA), and linear and brush analogs with controlled gradient and statistical sequence were synthesized by atom transfer radical polymerization (ATRP). The effect of sequence on self-healing in BA/MMA copolymer brush particle hybrids followed similar trends as for linear analogs. Most rapid restoration of mechanical properties was found for statistical copolymer sequence; an increase of the high Tg (MMA) component provided a path to raise the material's modulus while retaining self-heal ability. Creep testing revealed profound differences between linear and brush systems. While linear copolymers featured substantial viscous deformation when exposed to constant stress in the linear regime, brush analogs displayed minimal permanent deformation and featured shape restoration. The reduction of flow was interpreted to be a consequence of slow cooperative relaxation due to the complex microstructure of brush particle hybrids in which long-range motions are constrained through entanglements and slow-diffusing particle cores. The rubbery-like response imparts BA/MMA copolymer brush material systems concurrent "shape-memory" and "self-heal" capability. This ability to "recall-and-repair" could find application in the design of functional hybrid materials, for example, for soft robotics.