Thermoreversible [2 + 2] Photodimers of Monothiomaleimides and Intrinsically Recyclable Covalent Networks Thereof.

The development of intrinsically recyclable cross-linked materials remains challenged by the inherently unfavorable chemical equilibrium that dictates the efficiency of the reversible covalent bonding/debonding chemistry. Rather than having to (externally) manipulate the bonding equilibrium, we here introduce a new reversible chemistry platform based on monosubstituted thiomaleimides that can undergo complete and independent light-activated covalent bonding and on-demand thermal debonding above 120 °C. Specifically, repeated bonding/debonding of a small-molecule thiomaleimide [2 + 2] photodimer is demonstrated over five heat/light cycles with full conversion in both directions, thereby regenerating its initial monothiomaleimide constituents.

The Power of Action Plots: Unveiling Reaction Selectivity of Light-Stabilized Dynamic Covalent Chemistry.

Exploiting the optimum wavelength of reactivity for efficient photochemical reactions has been well-established based on the development of photochemical action plots. We herein demonstrate the power of such action plots by a remarkable example of the wavelength-resolved photochemistry of two triazolinedione (TAD) substrates, i.e.

Visible Light Conjugation with Triazolinediones as a Route to Degradable Poly(ethylene glycol)-Lipids for mRNA Lipid Nanoparticle Formulation.

Polyethylene glycol (PEG) is considered as the gold standard for colloidal stabilization of nanomedicines, yet PEG is non-degradable and lacks functionality on the backbone. Herein, we introduce concomitantly PEG backbone functionality and degradability via a one-step modification with 1,2,4-triazoline-3,5-diones (TAD) under green light. The TAD-PEG conjugates are degradable in aqueous medium under physiological conditions, with the rate of hydrolysis depending on pH and temperature.

Two Functions from a Single Photoresist: Tuning Microstructure Degradability from Light-Stabilized Dynamic Materials.

A photoresist-based on a light-stabilized dynamic material driven by an out-of-equilibrium photo-Diels-Alder reaction of triazolinediones with naphthalenes-whose ability to intrinsically degrade postprinting can be tuned by a simple adjustment of laser intensity during 3D laser lithography is introduced. The resist's ability to form stable networks under green light irradiation that degrade in the dark is transformed into a tunable degradable 3D printing material platform. In-depth characterization of the printed microstructures via atomic force microscopy before and during degradation reveals the high dependency of the final structures' properties on the writing parameters.

Photocrosslinking of Polyacrylamides Using [2 + 2] Photodimerisation of Monothiomaleimides.

The [2 + 2] photocycloaddition of monothiomaleimides (MTMs) has been exploited for the photocrosslinking of polyacrylamides. Polymer scaffolds composed of dimethylacrylamide and varying amounts of d,l-homocysteine thiolactone acrylamide (5, 10, and 20 mol %) were synthesized via free-radical polymerization, whereby the latent thiol functionality was exploited to incorporate MTM motifs. Subsequent exposure to UV light (λ = 365 nm, 15 mW cm) triggered intermolecular crosslinking via the photodimerization of MTM side chains, thus resulting in the formation of polyacrylamide gels.

Polymers without Petrochemicals: Sustainable Routes to Conventional Monomers.

Access to a wide range of plastic materials has been rationalized by the increased demand from growing populations and the development of high-throughput production systems. Plastic materials at low costs with reliable properties have been utilized in many everyday products. Multibillion-dollar companies are established around these plastic materials, and each polymer takes years to optimize, secure intellectual property, comply with the regulatory bodies such as the Registration, Evaluation, Authorisation and Restriction of Chemicals and the Environmental Protection Agency and develop consumer confidence.

Force-reversible chemical reaction at ambient temperature for designing toughened dynamic covalent polymer networks.

Force-reversible C-N bonds, resulting from the click chemistry reaction between triazolinedione (TAD) and indole derivatives, offer exciting opportunities for molecular-level engineering to design materials that respond to mechanical loads. Here, we displayed that TAD-indole adducts, acting as crosslink points in dry-state covalently crosslinked polymers, enable materials to display reversible stress-responsiveness in real time already at ambient temperature. Whereas the exergonic TAD-indole reaction results in the formation of bench-stable adducts, they were shown to dissociate at ambient temperature when embedded in a polymer network and subjected to a stretching force to recover the original products.

Reversible Transformations of Polymer Topologies through Visible Light and Darkness.

A fundamentally important characteristic of a macromolecule is its shape. Herein, visible light and darkness are used as the only stimuli to reversibly alter the topology of well-defined polymers in a one-pot procedure. For this, linear naphthalene-containing polyacrylates are used as scaffolds for the visible light-induced cycloaddition with various substituted triazolinediones (i.

Light-fueled dynamic covalent crosslinking of single polymer chains in non-equilibrium states.

While polymer synthesis proceeds predominantly towards the thermodynamic minimum, living systems operate on the reverse principle - consuming fuel to maintain a non-equilibrium state. Herein, we report the controlled formation of 3D macromolecular architectures based on light-fueled covalent non-equilibrium chemistry. In the presence of green light (525 nm) and a bivalent triazolinedione (TAD) crosslinker, naphthalene-containing polymers can be folded into single chain nanoparticles (SCNPs).

Shining Light on Poly(ethylene glycol): From Polymer Modification to 3D Laser Printing of Water Erasable Microstructures.

The implementation of stimuli-responsive bonds into 3D network assemblies is a key concept to design adaptive materials that can reshape and degrade. Here, a straightforward but unique photoresist is introduced for the tailored fabrication of poly(ethylene glycol) (PEG) materials that can be readily erased by water, even without the need for acidic or basic additives. Specifically, a new class of photoresist is developed that operates through the backbone crosslinking of PEG when irradiated in the presence of a bivalent triazolinedione.

From Sequence-Defined Macromolecules to Macromolecular Pin Codes.

Dynamic sequence-defined oligomers carrying a chemically written pin code are obtained through a strategy combining multicomponent reactions with the thermoreversible addition of 1,2,4-triazoline-3,5-diones (TADs) to indole substrates. The precision oligomers are specifically designed to be encrypted upon heating as a result of the random reshuffling of the TAD-indole covalent bonds within the backbone, thereby resulting in the scrambling of the encoded information. The encrypted pin code can eventually be decrypted following a second heating step that enables the macromolecular pin code to be deciphered using 1D electrospray ionization-mass spectrometry (ESI-MS).

Light-Stabilized Dynamic Materials.

The light-responsive adaptation of polymer materials typically requires different wavelengths or additional heat to induce reversible covalent bond formation and dissociation. Here, we bypass the use of invasive triggers by introducing light-stabilized dynamic materials that can undergo a repeatable change in topology from a covalently cross-linked material into a liquid polymer formulation by switching one visible light source on-and-off without the need for any additional triggers. Specifically, we exploit the photo-Diels-Alder reaction of triazolinediones with naphthalenes as a dynamic covalent cross-linking platform that enables green light-induced network formation, while the cross-linked material collapses through spontaneous cycloreversion upon standing in the dark at ambient temperature.

Controlling thermal reactivity with different colors of light.

The ability to switch between thermally and photochemically activated reaction channels with an external stimulus constitutes a key frontier within the realm of chemical reaction control. Here, we demonstrate that the reactivity of triazolinediones, powerful coupling agents in biomedical and polymer research, can be effectively modulated by an external photonic field. Specifically, we show that their visible light-induced photopolymerization leads to a quantitative photodeactivation, thereby providing a well-defined off-switch of their thermal reactivity.

Design of a thermally controlled sequence of triazolinedione-based click and transclick reactions.

The reaction of triazolinediones (TADs) and indoles is of particular interest for polymer chemistry applications, as it is a very fast and irreversible additive-free process at room temperature, but can be turned into a dynamic covalent bond forming process at elevated temperatures, giving a reliable bond exchange or 'transclick' reaction. In this paper, we report an in-depth study aimed at controlling the TAD-indole reversible click reactions through rational design of modified indole reaction partners. This has resulted in the identification of a novel class of easily accessible indole derivatives that give dynamic TAD-adduct formation at significantly lower temperatures.

Triazolinediones as Highly Enabling Synthetic Tools.

Triazolinediones (TADs) are unique reagents in organic synthesis that have also found wide applications in different research disciplines, in spite of their somewhat "exotic" reputation. In this review, we offer two case studies that demonstrate the possibilities of these versatile and reliable synthetic tools, namely, in the field of polymer science as well as in more recently emerging applications in the field of click chemistry. As the general use of triazolinediones has always been hampered by the limited commercial and synthetic availability of such reagents, we also offer a review of the available TAD reagents, together with a detailed discussion of their synthesis and reactivity.