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

β to α Form Transition Observed in the Crystalline Structures of Syndiotactic Polystyrene (sPS)

A solid−solid crystalline transition from β to α forms in syndiotactic polystyrene (sPS) was found during the mechanical deformation in the temperature range of 130−218 °C, studied by X-ray and infrared spectroscopy. α and β forms, in contrast to the other two crystalline structures (γ and δ forms) in sPS, are two major crystalline forms manufactured through a concise molding process which is industrially readily accessible. There have been a number of structural transitions found between two crystalline structures among the four different crystalline forms of sPS. In this work, β to α form transition at well below the melting temperature of sPS (∼270 °C) was found by mechanical deformation, which became more pronounced as temperature increased. The structural transition was intimately related to the crystallization temperature and the densities of α and β forms

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

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

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

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

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 Qβ 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

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