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The National Science Foundation

Center for the Chemistry of Molecularly Optimized NETworks

CRIPT

MONET Innovation efforts have spun off into CRIPT (the Community Resource for Innovation in Polymer Technology). CRIPT is a partnership between MIT, Citrine Informatics, Dow Chemical, NIST, and the University of Chicago that is taking our intellectual advances and the tools those advances led to, and extending them as a critical piece of a community database for polymer science through an NSF Phase I Convergence Accelerator project.

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Shear thinning of associative polymers is tied to bond breakage under deformation and retraction of dangling chains, as predicted by transient network theories. However, an in-depth understanding of the molecular mechanisms is limited by our ability to measure the molecular states of the polymers during deformation. Herein, utilizing a custom-built rheo-fluorescence setup, bond dissociation in model end-linked associative polymers is quantified in real time with nonlinear shear deformation based on a fluorescence quench transition when phenanthroline ligands bind with Ni2+. All of the networks exhibit shear thinning, and the dangling chain fraction increases with the shear rate. However, the number of broken bonds is smaller than that predicted by transient network theories, indicating additional relaxation modes or topological inhomogeneities in the networks. Through tuning counteranion chemistry, networks with similar relaxation times but varying dissociation and association rate constants (kd and ka) of Ni2+-phenanthroline cross-links are developed. Decreasing ka contributes to more dangling chain formation, while the effect of kd is less pronounced. Following force-accelerated bond dissociation of bridging chains, the dangling ends in networks with higher ka tend to reassociate to form elastically inactive loops, while the dangling chains are preserved in networks with lower ka. This indicates the critical role of bond reassociation kinetics in dictating shear-induced topological interchange of different chain configurations. Besides reaction kinetics, decreasing network junction functionality results in less shear thinning and broken bonds, originating from the lower amount of bond breakage required to flow and the higher tendency of the dissociated bonds to reform bridging chains.

We report that differences in ring strain enthalpy between cis and trans isomers of sila-cycloheptene provide a driving force for both polymerization and depolymerization via olefin metathesis. A need for new methods to reintroduce the low-strain isomer into the plastic economy inspired the development of a polymerization based on ring-opening/cross-metathesis step polymerization, which afforded perfect sequence control for an alternating copolymer. The chemical principles are a platform for achieving both efficient polymerization and depolymerization with high mass recovery in functional polymers.

In polymer mechanochemistry, mechanophores are specific molecular units within the macromolecular backbone that are particularly sensitive to tension. To facilitate understanding of this selective responsiveness, we introduce the restoring force triangle (RFT). The RFT is a mnemonic device intended to provide intuitive insight into how external tensile forces (i.e., stretching) can selectively activate scissile bonds, thereby initiating mechanically driven chemical reactions. The RFT utilizes two easily computable parameters: the effective bond stiffness constant, which measures a bond’s resistance to elongation, and the bond dissociation energy, which is the energy required to break a bond. These parameters help categorize reactivity into thermal and mechanical domains, providing a useful framework for developing new mechanophores that are responsive to force but thermally stable. The RFT helps chemists intuitively understand how tensile force contributes to the activation of a putative mechanophore, facilitating the development of mechanochemical reactions and mechano-responsive materials.

We established a strain learning mechanical metamaterial that can not only recover after plastic deformation but also become stronger and stiffer in response to the applied loads. We demonstrate that shape-memory protein–polymer networks can unravel to release their stored length and, after recovery, will reconfigure to accommodate higher loads. These materials are incorporated into lattice frameworks using additive manufacturing which are then shown to become up to 2.5× stiffer after being crushed to 80% strain and recovered. This strain learning behavior enables the creation of metamaterials that are “teachable” and can autonomously remodel in response to applied loads, similar to the processes that occur in natural materials.

Aggregation-induced emission luminogens (AIEgens) that respond to mechanical force are increasingly used as force probes, memory devices, and advanced security systems. Most of the known mechanisms to modulate mechanoresponsive AIEgens have been based on changes in aggregation states, involving only physical alterations. Instances that employ covalent bond cleavage are still rare. We have developed a novel mechanochemical uncaging strategy to unveil AIEgens with diverse emission characteristics using engineered norborn-2-en-7-one (NEO) mechanophores. These NEO mechanophores were covalently integrated into polymer molecules and activated in both the solution and solid states. This activation resulted in highly tunable fluorescence upon immobilization through solidification or aggregation, producing blue, green, yellow, and orange-red emissions. By designing the caged and uncaged forms as donor–acceptor pairs for Förster resonance energy transfer (FRET), we achieved multicolor mechanofluorescence, effectively broadening the color spectrum to include white emission. Additionally, we computationally explored the electronic structures of activated NEOs, providing insights into the observed regiochemical effects of the substituents. This understanding, together with the novel luminogenic characteristics of the caged and activated species, provides a highly tunable reporter that traces progress with continuous color evolution. This advancement paves the way for future applications of mechanoresponsive materials in areas like damage detection and bioimaging.

Thermoset toughness and deconstructability are often opposing features; simultaneously improving both without sacrificing other mechanical properties (e.g., stiffness and tensile strength) is difficult, but, if achieved, could enhance the usage lifetime and end-of-life options for these materials. Here, a strategy that addresses this challenge in the context of photopolymer resins commonly used for 3D printing of glassy, acrylic thermosets is introduced. It is shown that incorporating bis-acrylate “transferinkers,” which are cross-linkers capable of undergoing degenerative chain transfer and new strand growth, as additives (5–25 mol%) into homemade or commercially available photopolymer resins leads to photopolymer thermosets with substantially improved tensile toughness and triggered chemical deconstructability with minimal impacts on Young's moduli, tensile strengths, and glass transition temperatures. These properties result from a transferinker-driven topological transition in network structure from the densely cross-linked long, heterogeneous primary strands of traditional photopolymer networks to more uniform, star-like networks with few dangling ends; the latter structure more effectively bear stress yet is also more easily depercolated via solvolysis. Thus, transferinkers represent a simple and effective strategy for improving the mechanical properties of photopolymer thermosets and providing a mechanism for their triggered deconstructability.

In this work, we introduce a 3D-printable virus-like particle (VLP)-enhanced cross-linked biopolymer system. VLPs displaying surface-available acrylate groups were prepared through aza-Michael addition to serve as resins. The VLP resins were then photopolymerized into a poly(ethylene glycol) diacrylate (PEGDA) network following DLP 3D printing. This approach represents a convergence of disciplines, where the synergistic interaction between virology and additive manufacturing unlocks new frontiers in biotechnology.

The aza Paternò–Büchi reaction is a [2+2]-cycloaddition reaction between imines and alkenes that produces azetidines, four-membered nitrogen-containing heterocycles. Currently, successful examples rely primarily on either intramolecular variants or cyclic imine equivalents. To unlock the full synthetic potential of aza Paternò–Büchi reactions, it is essential to extend the reaction to acyclic imine equivalents. Here, we report that matching of the frontier molecular orbital energies of alkenes with those of acyclic oximes enables visible light–mediated aza Paternò–Büchi reactions through triplet energy transfer catalysis. The utility of this reaction is further showcased in the synthesis of epi-penaresidin B. Density functional theory computations reveal that a competition between the desired [2+2]-cycloaddition and alkene dimerization determines the success of the reaction. Frontier orbital energy matching between the reactive components lowers transition-state energy (ΔGǂ) values and ultimately promotes reactivity.

Plant virus-like particles (VLPs) are biocompatible, non-infectious nanomaterials with promising applications as immunotherapeutics and vaccines. However, slow-release VLP formulations are needed to achieve long-term efficacy without repeated administration. VLP hydrogels allow the encapsulation and sustained delivery of VLPs, but the particles must covalently bind the hydrogel polymers to avoid premature loss. This has been achieved so far by in situ VLP polymerization, which requires high viral concentrations (5–10 mg/mL, 0.5–1 wt%) to form stable hybrid VLP–hydrogel networks and this complicates scalability and clinical translation. Here, we developed a novel swell-and-click method that led to successful VLP scaffold formation regardless of the viral load used. As a result, VLP-functionalized hydrogels were fabricated with viral concentrations as low as 0.1–1 mg/mL (0.01–0.1 % wt%) without compromising the scaffold stability on the process. The hydrogels incorporate VLPs during swelling, followed by copper-free click chemistry reactions that bind the particles covalently to the polymer. The swell-and-click method also resulted in more than a two-fold enhancement in VLP uptake into the hydrogels and it provides a means of combined burst release and prolonged sustained release, desired traits for cancer immunotherapy treatment. The present work introduces a novel methodology for the design of VLP-based hydrogels, which could facilitate the scalability of the fabrication process and move a significant step forward towards clinical translation of long-term VLP vaccination in cancer disease.

Mechanical force drives distinct chemical reactions; yet, its vectoral nature results in complicated coupling with reaction trajectories. Here, we utilize a physical organic model inspired by the classical Morse potential and its differential forms to identify effective force constant (keff) and reaction energy (ΔE) as key molecular features that govern mechanochemical kinetics. Through a comprehensive experimental and computational investigation with four norborn-2-en-7-one (NEO) mechanophores, we establish the relationship between these features and the force-dependent energetic changes along the reaction pathways. We show that the complex kinetic behavior of the tensioned bonds is generally and quantitatively predicted by a simple multivariate linear regression based on the two easily computed features with a straightforward workflow. These results demonstrate a general mechanistic framework for mechanochemical reactions under tensile force and provide a highly accessible tool for the large-scale computational screening in the design of mechanophores.

Gels made of telechelic polymers connected by reversible cross-linkers are a versatile design platform for biocompatible viscoelastic materials. Their linear response to a step strain displays a fast, near-exponential relaxation when using low-valence cross-linkers, while larger supramolecular cross-linkers bring about much slower dynamics involving a wide distribution of timescales whose physical origin is still debated. Here, we propose a model where the relaxation of polymer gels in the dilute regime originates from elementary events in which the bonds connecting two neighboring cross-linkers all disconnect. Larger cross-linkers allow for a greater average number of bonds connecting them but also generate more heterogeneity. We characterize the resulting distribution of relaxation timescales analytically and accurately reproduce stress relaxation measurements on metal-coordinated hydrogels with a variety of cross-linker sizes including ions, metal-organic cages, and nanoparticles. Our approach is simple enough to be extended to any cross-linker size and could thus be harnessed for the rational design of complex viscoelastic materials.

Supramolecular polymer networks contain non-covalent cross-links that enable access to broadly tunable mechanical properties and stimuli-responsive behaviors; the incorporation of multiple unique non-covalent cross-links within such materials further expands their mechanical responses and functionality. To date, however, the design of such materials has been accomplished through discrete combinations of distinct interaction types in series, limiting materials design logic. Here we introduce the concept of leveraging “nested” supramolecular crosslinks, wherein two distinct types of non-covalent interactions exist in parallel, to control bulk material functions. To demonstrate this concept, we use polymer-linked Pd2L4 metal–organic cage (polyMOC) gels that form hollow metal–organic cage junctions through metal–ligand coordination and can exhibit well-defined host-guest binding within their cavity. In these “nested” supramolecular network junctions, the thermodynamics of host-guest interactions within the junctions affect the metal–ligand interactions that form those junctions, ultimately translating to substantial guest-dependent changes in bulk material properties that could not be achieved in traditional supramolecular networks with multiple interactions in series.

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