De novo DNA-based catch bonds.

All primary chemical interactions weaken under mechanical stress, which imposes fundamental mechanical limits on the materials constructed from them. Biological materials combine plasticity with strength, for which nature has evolved a unique solution-catch bonds, supramolecular interactions that strengthen under tension. Biological catch bonds use force-gated conformational switches to convert weak bonds into strong ones.

SI-PET-RAFT in flow: improved control over polymer brush growth.

Surface-initiated photoinduced electron transfer-reversible addition-fragmentation chain transfer (SI-PET-RAFT) provides a light-dependent tool to synthesize polymer brushes on different surfaces that tolerates oxygen and water, and does not require a metal catalyst. Here we introduce improved control over SI-PET-RAFT polymerizations continuous flow conditions. We confirm the composition and topological structure of the brushes by X-ray photoelectron spectroscopy, ellipsometry, and AFM.

Single-Molecule Force Spectroscopy of a Tetraaryl Succinonitrile Mechanophore.

Fluorescent damage reporters that use mechanochemical activation of a covalent bond to elicit an optical signal are emerging tools in material mechanics as a means to access the nanoscale distribution of forces inside materials under stress. A promising class of damage reporters are tetraaryl succinonitriles (TASN), whose mechanical activation results in stable fluorescent radical species. However, in-depth insights into the molecular mechanics of TASN activation are absent, precluding their use as quantitative mechanoprobes.

Optical tweezer measurements of asymptotic nonlinearities in complex fluids.

This article presents micro-medium-amplitude oscillatory shear (μMAOS), a method to measure the frequency-dependent micromechanical properties of soft materials in the asymptotically nonlinear regime using optical tweezers. We have developed a theoretical framework to extract these nonlinear mechanical properties of the material from experimental measurements and also proposed a physical interpretation of the third-order nonlinearities measured in single-tone oscillatory tests. We validate the method using a well-characterized surfactant solution of wormlike micelles, and subsequently employ this technique to demonstrate that the cytoplasm of a living cell undergoes strain softening and shear thinning when locally subjected to weakly nonlinear oscillatory deformations.

Allosteric pathway selection in templated assembly.

Assembling large numbers of molecular building blocks into functional nanostructures is no trivial task. It relies on guiding building blocks through complex energy landscapes shaped by synergistic and antagonistic supramolecular interactions. In nature, the use of molecular templates is a potent strategy to navigate the process to the desired structure with high fidelity.