A Thermally Stable SO2-Releasing Mechanophore: Facile Activation, Single-Event Spectroscopy, and Molecular Dynamic Simulations.

Polymers that release small molecules in response to mechanical force are promising candidates as next-generation on-demand delivery systems. Despite advancements in the development of mechanophores for releasing diverse payloads through careful molecular design, the availability of scaffolds capable of discharging biomedically significant cargos in substantial quantities remains scarce. In this report, we detail a nonscissile mechanophore built from an 8-thiabicyclo[3.2.1]octane 8,8-dioxide (TBO) motif that releases one equivalent of sulfur dioxide (SO2) from each repeat unit. The TBO mechanophore exhibits high thermal stability but is activated mechanochemically using solution ultrasonication in either organic solvent or aqueous media with up to 63% efficiency, equating to 206 molecules of SO2 released per 143.3 kDa chain. We quantified the mechanochemical reactivity of TBO by single-molecule force spectroscopy and resolved its single-event activation. The force-coupled rate constant for TBO opening reaches ∼9.0 s-1 at ∼1520 pN, and each reaction of a single TBO domain releases a stored length of ∼0.68 nm. We investigated the mechanism of TBO activation using ab initio steered molecular dynamic simulations and rationalized the observed stereoselectivity. These comprehensive studies of the TBO mechanophore provide a mechanically coupled mechanism of multi-SO2 release from one polymer chain, facilitating the translation of polymer mechanochemistry to potential biomedical applications.

Virus-like Particles Armored by an Endoskeleton.

Many virus-like particles (VLPs) have good chemical, thermal, and mechanical stabilities compared to those of other biologics. However, their stability needs to be improved for the commercialization and use in translation of VLP-based materials. We developed an endoskeleton-armored strategy for enhancing VLP stability. Specifically, the VLPs of physalis mottle virus (PhMV) and Qß were used to demonstrate this concept. We built an internal polymer "backbone" using a maleimide-PEG15-maleimide cross-linker to covalently interlink viral coat proteins inside the capsid cavity, while the native VLPs are held together by only noncovalent bonding between subunits. Endoskeleton-armored VLPs exhibited significantly improved thermal stability (95 °C for 15 min), increased resistance to denaturants (i.e., surfactants, pHs, chemical denaturants, and organic solvents), and enhanced mechanical performance. Single-molecule force spectroscopy demonstrated a 6-fold increase in rupture distance and a 1.9-fold increase in rupture force of endoskeleton-armored PhMV. Overall, this endoskeleton-armored strategy provides more opportunities for the development and applications of materials.

Strain-triggered acidification in a double-network hydrogel enabled by multi-functional transduction of molecular mechanochemistry.

Recent work has demonstrated that force-triggered mechanochemical reactions within a polymeric material are capable of inducing measurable changes in macroscopic material properties, but examples of bulk property changes without irreversible changes in shape or structure are rare. Here, we report a double-network hydrogel that undergoes order-of-magnitude increases in acidity when strained, while recovering its initial shape after large deformation. The enabling mechanophore design is a 2-methoxy-gem-dichlorocyclopropane mechanoacid that is gated within a fused methyl methoxycyclobutene carboxylate mechanophore structure. This gated mechanoacid is incorporated via radical co-polymerization into linear and network polymers. Sonication experiments confirm the mechanical release of HCl, and single-molecule force spectroscopy reveals enhanced single-molecular toughness in the covalent strand. These mechanochemical functions are incorporated into a double-network hydrogel, leading to mechanically robust and thermally stable materials that undergo strain-triggered acid release. Both quasi-static stretching and high strain rate uniaxial compression result in substantial acidification of the hydrogel, from pH ∼ 7 to ∼5.

Mechanochemistry of Cubane.

We report the mechanochemical reactivity of the highly strained pentacyclic hydrocarbon cubane. The mechanical reactivity of cubane is explored for three regioisomers with 1,2-, 1,3-, and 1,4-substituted pulling attachments. Whereas all compounds can be activated thermally, mechanical activation is observed via pulsed ultrasonication of cubane-containing polymers only when force is applied via 1,2-attachment. The single observed product of the force-coupled reaction is a thermally inaccessible syn-tricyclooctadiene, in contrast to cyclooctatetraene (observed thermally) or a pair of cyclobutadienes that would result from sequential cyclobutane scission. We further quantify the mechanochemical reactivity of cubane by single molecule force spectroscopy, and force-coupled rate constants for ring opening reach ∼33 s-1 at a force of ∼1.55 nN, lower than forces of 1.8-2.0 nN that are typical of conventional cyclobutanes.

Toughening hydrogels through force-triggered chemical reactions that lengthen polymer strands.

The utility and lifetime of materials made from polymer networks, including hydrogels, depend on their capacity to stretch and resist tearing. In gels and elastomers, those mechanical properties are often limited by the covalent chemical structure of the polymer strands between cross-links, which is typically fixed during the material synthesis. We report polymer networks in which the constituent strands lengthen through force-coupled reactions that are triggered as the strands reach their nominal breaking point. In comparison with networks made from analogous control strands, reactive strand extensions of up to 40% lead to hydrogels that stretch 40 to 50% further and exhibit tear energies that are twice as large. The enhancements are synergistic with those provided by double-network architectures and complement other existing toughening strategies.

Mechanical Property of Polypropylene Gels Associated with That of Molten Polypropylenes.

This study aims to understand the fundamental mechanical relationship between polypropylene (PP)-gels and solid PPs without solvent through mechanical and thermal analyses, by which the mechanical similarities between molten PPs and PP gels were found, leading to the reliable estimate of the mechanical properties of semi-crystalline gels. The gelation of syndiotactic and isotactic polypropylenes (sPP and iPP) was found when PPs were dissolved in 1,2,3,4-tetrahydronaphthalene (tetralin). Interestingly, it was found that the storage modulus of sPP-gel became higher than that of iPP-gel at low PP concentration (<~40 wt%). The result was distinctly different from the result of neat solid PPs (without solvent), where the modulus of solid sPP is generally significantly lower than that of solid iPP. Such inversion behavior in the mechanical property of semi-crystalline gels had not been reported and discussed before. By further investigation of the storage moduli of neat sPP and iPP, it was found that the storage modulus of sPP became higher than that of iPP above the melting points of PP, which was similar to the behavior of the storage moduli observed in the diluted PP-gels. Such similarity between PP-gels and PP melts was also observed within iPP samples with different molecular weights.

Molecular Characterization of Polymer Networks.

Polymer networks are complex systems consisting of molecular components. Whereas the properties of the individual components are typically well understood by most chemists, translating that chemical insight into polymer networks themselves is limited by the statistical and poorly defined nature of network structures. As a result, it is challenging, if not currently impossible, to extrapolate from the molecular behavior of components to the full range of performance and properties of the entire polymer network. Polymer networks therefore present an unrealized, important, and interdisciplinary opportunity to exert molecular-level, chemical control on material macroscopic properties. A barrier to sophisticated molecular approaches to polymer networks is that the techniques for characterizing the molecular structure of networks are often unfamiliar to many scientists. Here, we present a critical overview of the current characterization techniques available to understand the relation between the molecular properties and the resulting performance and behavior of polymer networks, in the absence of added fillers. We highlight the methods available to characterize the chemistry and molecular-level properties of individual polymer strands and junctions, the gelation process by which strands form networks, the structure of the resulting network, and the dynamics and mechanics of the final material. The purpose is not to serve as a detailed manual for conducting these measurements but rather to unify the underlying principles, point out remaining challenges, and provide a concise overview by which chemists can plan characterization strategies that suit their research objectives. Because polymer networks cannot often be sufficiently characterized with a single method, strategic combinations of multiple techniques are typically required for their molecular characterization.

Harnessing Multiple Surface Deformation Modes for Switchable Conductivity Surfaces.

Surface deformation modes, such as wrinkling, creasing, and cracking, enable a plethora of surface morphologies under mechanical loading, which have been widely exploited to provide flexibility and stretchability to electronic devices. As each phenomenon offers a distinct set of potential advantages, controlling the types and spatial locations of deformation modes is key for their successful application. In this study, we demonstrate a method to simultaneously harness multiple surface deformation modes-wrinkles, creases, and cracks-in patterned multilayer films. The wrinkling of metal-coated stiff patterned films provides flexibility and stretchability, while the reversible formation of creases in the intervening regions of the bare elastomer is used to template the formation of patterned cracks in the metal. While conventional cracks can be difficult to precisely control, the patterned cracks demonstrated here remain straight over long distances and show tunable lateral spacings from hundreds of micrometers to centimeters. Finally, the reversible opening and closing of these cracks under mechanical loading provides mechanically gated electrical switches with small and tunable critical switching strains of 0.05-0.18 and high on/off ratios of >107, enabling the preparation of mechanical NAND and NOR logic gates each composed of multiple patterned switches on a single elastomer surface.

Elastocapillary Crease.

A material under compression often forms creases. When the material is elastic and soft, the nucleation of creases depends on both elasticity and capillarity. Here we introduce a model of elastocapillary creases. The model assumes that the surface tension remains constant on the free surface, but may change upon self-contact. In particular, surface tension vanishes upon self-contact for a pristine surface of elastomers and gels. The model predicts that the nucleation of creases depends on the sizes of surface defects relative to the elastocapillary length, and happens over a well-defined range of strains, instead of a specific strain. The loss of surface tension upon self-contact lowers the energy barrier for nucleation, and widens the range of nucleation strains for materials of any thickness relative to the elastocapillary length. We test this model by conducting experiments with materials of various elastocapillary lengths, along with the data available in the literature.

Effects of Stiff Film Pattern Geometry on Surface Buckling Instabilities of Elastic Bilayers.

Buckling instabilities-such as wrinkling and creasing-of micropatterned elastic surfaces play important roles in applications, including flexible electronics and microfluidics. In many cases, the spatial dimensions associated with the imposed pattern can compete with the natural length scale of the surface instabilities (e.g., the wrinkle wavelength), leading to a rich array of surface buckling behaviors. In this paper, we consider elastic bilayers consisting of a spatially patterned stiff film supported on a continuous and planar soft substrate. Through a combination of experimental and computational analyses, we find that three surface instability modes-wrinkling, Euler buckling, and rigid rotation-are observed for the stiff material patterns, depending on the in-plane dimensions of the film compared to the natural wrinkle wavelength, while the intervening soft regions undergo a creasing instability. The interplay between these instabilities leads to a variety of surface structures as a function of the pattern geometry and applied compressive strain, in many cases yielding contact between neighboring stiff material elements because of the formation of creases in the gaps between them.

Measuring the Elastic Modulus of Thin Polymer Sheets by Elastocapillary Bending.

We describe bending by liquid/liquid or liquid/air interfaces as a simple and broadly applicable technique for measuring the elastic modulus of thin elastic sheets. The balance between bending and surface energies allows for the characterization of a wide range of materials with moduli ranging from kilopascals to gigapascals in both vapor and liquid environments, as demonstrated here by measurements of both soft hydrogel layers and stiff glassy polymer films. Compared to existing approaches, this method is especially useful for characterizing soft materials (