Light-driven polymer recycling to monomers and small molecules.

Only a small proportion of global plastic waste is recycled, of which most is mechanically recycled into lower quality materials. The alternative, chemical recycling, enables renewed production of pristine materials, but generally comes at a high energy cost, particularly for processes like pyrolysis. This review focuses on light-driven approaches for chemically recycling and upcycling plastic waste, with emphasis on reduced energy consumption and selective transformations not achievable with heat-driven methods. We focus on challenging to recycle backbone structures composed of mainly C‒C bonds, which lack functional groups i.e., esters or amides, that facilitate chemical recycling e.g., by solvolysis. We discuss the use of light, either in conjunction with heat to drive depolymerization to monomers or via photocatalysis to transform polymers into valuable small molecules. The structural prerequisites for these approaches are outlined, highlighting their advantages as well as limitations. We conclude with an outlook, addressing key challenges, opportunities, and provide guidelines for future photocatalyst (PC) development.

Design of an Oxygen-Tolerant Photo-RAFT System for Protein-Polymer Conjugation Achieving High Bioactivity.

Protein-polymer conjugates have significant potential in pharmaceutical and biomedical applications. To enable their widespread use, robust conjugation techniques are crucial. This study introduces a photo-initiated reversible addition-fragmentation chain-transfer (Photo-RAFT) polymerization system that exhibits excellent oxygen tolerance. This system allows for the synthesis of protein-polymer conjugates with high bioactivity under mild and aerobic conditions. Three photocatalytic systems utilizing Eosin Y (EY) as the photocatalyst with two different cocatalysts (ascorbic acid and triethanolamine) were investigated, each generating distinct reactive oxygen species (ROS) such as singlet oxygen, superoxide, hydrogen peroxide, and hydroxyl radicals. The impact of these ROS on three model proteins (lysozyme, albumin, and myoglobin) was evaluated, demonstrating varying bioactivities based on the ROS produced. The EY/TEOA system was identified as the optimal photo-RAFT initiating system, enabling the preparation of protein-polymer conjugates under aerobic conditions while maintaining high protein enzymatic activity. To showcase the potential of this approach, lysozyme-poly(dimethylaminoethyl acrylate) conjugates were successfully prepared and exhibited enhanced antimicrobial property against Gram-positive and Gram-negative bacteria.

Photo-RAFT Polymerization for Hydrogel Synthesis through Barriers and Development of Light-Regulated Healable Hydrogels under NIR Irradiation.

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 of its fast polymerization rates and high oxygen tolerance, this system is successfully applied for the preparation of hydrogels. Exploiting the enhanced penetration of NIR light, photoinduced gelation is effectively performed through non-transparent biological barriers. Notably, the RAFT agents embedded in these hydrogel networks can be reactivated on-demand, enabling the hydrogel healing under NIR light irradiation. In contrast to the minimal healing capability (<15 %) of hydrogels prepared by free radical polymerization (FRP), RAFT-mediated networks display more than 80 % recovery of tensile strength. Although healable polymer networks under UV and blue lights have already been established, this work is the first photochemistry system using NIR light, facilitating photoinduced healing of hydrogels through thick non-transparent barriers.

Polymeric Amines Induce Nitric Oxide Release from S-Nitrosothiols.

Catalytic generation of nitric oxide (NO) from NO donors by nanomaterials has enabled prolonged NO delivery for various biomedical applications, but this approach requires laborious synthesis routes. In this study, a new class of materials, that is, polymeric amines including polyethyleneimine (PEI), poly-L-lysine, and poly(allylamine hydrochloride), is discovered to induce NO generation from S-nitrosothiols (RSNOs) at physiological conditions. Controlled NO generation can be readily achieved by tuning the concentration of the NO donors (RSNOs) and polymers, and the type and molecular weight of the polymers. Importantly, the mechanism of NO generation by these polymers is deciphered to be attributed to the nucleophilic reaction between primary amines on polymers and the SNO groups of RSNOs. The NO-releasing feature of the polymers can be integrated into a suite of materials, for example, simply by embedding PEI into poly(vinyl alcohol) (PVA) hydrogels. The functionality of the PVA/PEI hydrogels is demonstrated for Pseudomonas aeruginosa biofilm prevention with a ≈4 log reduction within 6 h. As NO has potential therapeutic implications in various diseases, the identification of polymeric amines to induce NO release will open new opportunities in NO-generating biomaterials for antibacterial, antiviral, anticancer, antithrombotic, and wound healing applications.

Selective Photoactivation of Trithiocarbonates Mediated by Metal Naphthalocyanines and Overcoming Activation Barriers Using Thermal Energy.

Metal naphthalocyanines (MNcs) were demonstrated to be efficient photocatalysts to activate photoinduced electron-transfer reversible addition-fragmentation chain transfer (PET-RAFT) polymerization, enabling well-controlled polymerization of (meth)acrylates under near-infrared (λ = 780 nm) light. Owing to their lower redox potential compared to previously explored photocatalysts, the activation of trithiocarbonate RAFT agents exhibited a unique selectivity that was dependent on the nature of the R group. Specifically, MNcs were capable in activating tertiary R group trithiocarbonates, whereas no activation of the trithiocarbonate possessing a secondary R group was observed. The combination of density functional theory calculations and experimental studies have revealed new mechanistic insights into the factors governing a PET-RAFT mechanism and explained this unique selectivity of MNcs toward tertiary carbon trithiocarbonates. Interestingly, by increasing the reaction temperature moderately (i.e., ∼15 °C), the energy barrier prohibiting the photoactivation of the trithiocarbonate with a secondary R group was overcome, enabling their successful activation.

Polydopamine Shell as a Ga3+ Reservoir for Triggering Gallium-Indium Phase Separation in Eutectic Gallium-Indium Nanoalloys.

Low melting point eutectic systems, such as the eutectic gallium-indium (EGaIn) alloy, offer great potential in the domain of nanometallurgy; however, many of their interfacial behaviors remain to be explored. Here, a compositional change of EGaIn nanoalloys triggered by polydopamine (PDA) coating is demonstrated. Incorporating PDA on the surface of EGaIn nanoalloys renders core-shell nanostructures that accompany Ga-In phase separation within the nanoalloys. The PDA shell keeps depleting the Ga3+ from the EGaIn nanoalloys when the synthesis proceeds, leading to a Ga3+-coordinated PDA coating and a smaller nanoalloy. During this process, the eutectic nanoalloys turn into non-eutectic systems that ultimately result in the solidification of In when Ga is fully depleted. The reaction of Ga3+-coordinated PDA-coated nanoalloys with nitrogen dioxide gas is presented as an example for demonstrating the functionality of such hybrid composites. The concept of phase-separating systems, with polymeric reservoirs, may lead to tailored materials and can be explored on a variety of post-transition metals.

2D Porphyrinic Metal-Organic Framework Nanosheets as Multidimensional Photocatalysts for Functional Materials.

Ultrathin porphyrinic 2D MOFs, ZnTCPP nanosheets (TCPP: 5,10,15,20-(tetra-4-carboxyphenyl) porphyrin) were employed as heterogeneous photocatalysts to activate PET-RAFT polymerization under various wavelengths ranging from violet to orange light. High polymerization rates, oxygen tolerance, and precise temporal control were achieved. The polymers showed narrow molecular weight distributions and good chain-end fidelity. The 2D ZnTCPP nanosheets were applied as photocatalysts in stereolithographic 3D printing in an open-air environment under blue light to yield well-defined 3D printed objects. Apart from providing an efficient catalytic system, 2D ZnTCPP nanosheets reinforced the mechanical properties of the 3D printed materials. The presence of ZnTCPP embedded in the materials conferred effective antimicrobial activity under visible light by production of singlet oxygen, affording 98 % and 93 % anti-bacterial efficiency against Gram-positive and Gram-negative bacteria, respectively.

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

Biofilms are a persistent issue in healthcare and industry. Once formed, the eradication of biofilms is challenging as the extracellular polymeric matrix provides protection against harsh environmental conditions and physically enhances resistance to antimicrobials. The fabrication of polymer brush coatings provides a versatile approach to modify the surface to resist the formation of biofilms. Herein, the authors report a facile synthetic route for the preparation of surface-tethered polymeric brushes with antifouling and visible light activated bactericidal properties using surface-initiated photoinduced electron transfer-reversible addition-fragmentation chain transfer polymerization (SI-PET-RAFT). Bactericidal property via the generation of singlet oxygen, which can be temporally and spatially controlled, is investigated against both Gram-positive and Gram-negative bacteria. In addition, the antibacterial properties of the surface can be recycled. This work paves the way for the preparation of polymer films that can resist and kill bacterial biofilms.

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

We report a high-throughput method for producing surface-tethered polymeric brushes on glass substrates via surface-initiated photoinduced electron transfer-reversible addition-fragmentation chain transfer polymerization (SI-PET-RAFT). Due to its excellent oxygen tolerance, SI-PET-RAFT allows brush growth using low reagent volumes (30 µL) without prior degassing. An initial 28 homopolymer brush library was successfully prepared and screened with respect to their antifouling performance. The high-throughput approach was further exploited to expand the library to encompass statistical, gradient, and block architectures to investigate the effect of monomer composition and distribution using two monomers of disparate performance. In this manner, the degree of attachment from Gram-negative Pseudomonas aeruginosa (PA) bacterial biofilms could be tuned between the bounds set by the homopolymer brushes.

An Oxygen-Tolerant PET-RAFT Polymerization for Screening Structure-Activity Relationships.

The complexity of polymer-protein interactions makes rational design of the best polymer architecture for any given biointerface extremely challenging, and the high throughput synthesis and screening of polymers has emerged as an attractive alternative. A porphyrin-catalysed photoinduced electron/energy transfer-reversible addition-fragmentation chain-transfer (PET-RAFT) polymerisation was adapted to enable high throughput synthesis of complex polymer architectures in dimethyl sulfoxide (DMSO) on low-volume well plates in the presence of air. The polymerisation system shows remarkable oxygen tolerance, and excellent control of functional 3- and 4-arm star polymers. We then apply this method to investigate the effect of polymer structure on protein binding, in this case to the lectin concanavalin A (ConA). Such an approach could be applied to screen the structure-activity relationships for any number of polymer-protein interactions.

2-(Methylthio)ethyl Methacrylate: A Versatile Monomer for Stimuli Responsiveness and Polymerization-Induced Self-Assembly in the Presence of Air.

In this communication, we investigate the photoinduced electron/energy transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization of 2-(methylthio)ethyl methacrylate (MTEMA) using 5,10,15,20-tetraphenylporphine zinc (ZnTPP) as a photocatalyst under visible red light (λmax = 635 nm). Interestingly, the polymerization kinetics were not affected by the presence of air as near identical polymerization kinetics were observed for non-deoxygenated and deoxygenated systems, which is attributed to the singlet oxygen quenching ability of MTEMA. In both cases, well-defined polymers were obtained with good control over the molecular weight and molecular weight distribution (MWD). Furthermore, we have demonstrated that MTEMA can undergo the polymerization-induced self-assembly (PISA) process from a poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) macromolecular chain transfer agent (macro-CTA) to yield well-defined polymeric nanoparticles of various morphologies. These nanoparticles were rapidly disassembled after exposure to visible light due to the formation of singlet oxygen by the encapsulated ZnTPP and subsequent rapid oxidation of the thioether group.