Peter D. Olmsted

Pulling geometry defines the mechanical resistance of a β-sheet protein

Proteins show diverse responses when placed under mechanical stress. The molecular origins of their differing mechanical resistance are still unclear, although the orientation of secondary structural elements relative to the applied force vector is thought to have an important function. Here, by using a method of protein immobilization that allows force to be applied to the same all-β protein, E2lip3, in two different directions, we show that the energy landscape for mechanical unfolding is markedly anisotropic. These results, in combination with molecular dynamics (MD) simulations, reveal that the unfolding pathway depends on the pulling geometry and is associated with unfolding forces that differ by an order of magnitude. Thus, the mechanical resistance of a protein is not dictated solely by amino acid sequence, topology or unfolding rate constant, but depends critically on the direction of the applied extension.

Microscopic Viscoelasticity: Shear Moduli of Soft Materials Determined from Thermal Fluctuations

We describe a high-resolution, high-bandwidth technique for determining the local viscoelasticity of soft materials such as polymer gels. Loss and storage shear moduli are determined from the power spectra of thermal fluctuations of embedded micron-sized probe particles, observed with an interferometric microscope. This provides a passive, small-amplitude measurement of rheological properties over a much broader frequency range than previously accessible to microrheology. We study both F-actin biopolymer solutions and polyacrylamide (PAAm) gels, as model semiflexible and flexible systems, respectively. We observe high-frequency

Spinodal-assisted crystallization in polymer melts

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Johnson–Segalman model with a diffusion term in cylindrical Couette flow

scaling of the shear modulus in F-actin solutions, in contrast to

Simulation Studies of Stratum Corneum Lipid Mixtures

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Flow phase diagrams for concentration-coupled shear banding.

scaling for PAAm.

Spatiotemporal Oscillations and Rheochaos in a Simple Model of Shear Banding

Recent experiments in some polymer melts quenched below the melting temperature have reported spinodal kinetics in small-angle x-ray scattering before the emergence of a crystalline structure. To explain these observations we propose that the coupling between density and chain conformation induces a liquid-liquid binodal within the equilibrium liquid-crystalline solid coexistence region. A simple phenomenological theory is developed to illustrate this idea, and several experimentally testable consequences are discussed. Shear is shown to enhance the kinetic role of the hidden binodal.

Coexistence and phase separation in sheared complex fluids

We study the Johnson–Segalman (JS) model as a paradigm for some complex fluids which are observed to phase separate, or “shear band” in flow. We analyze the behavior of this model in cylindrical Couette flow and demonstrate the history dependence inherent in the local JS model. We add a simple gradient term to the stress dynamics and demonstrate how this term breaks the degeneracy of the local model and prescribes a much smaller (discrete, rather than continuous) set of banded steady state solutions. We investigate some of the effects of the curvature of Couette flow on the observable steady state behavior and kinetics, and discuss some of the implication for metastability.

Mechanically unfolding proteins: The effect of unfolding history and the supramolecular scaffold

We present atomistic molecular dynamics results for fully hydrated bilayers composed of ceramide NS-24:0, free fatty acid 24:0 and cholesterol, to address the effect of the different components in the stratum corneum (the outermost layer of skin) lipid matrix on its structural properties. Bilayers containing ceramide molecules show higher in-plane density and hence lower rate of passive transport compared to phospholipid bilayers. At physiological temperatures, for all composition ratios explored, the lipids are in a gel phase with ordered lipid tails. However, the large asymmetry in the lengths of the two tails of the ceramide molecule leads to a fluidlike environment at the bilayer midplane. The lateral pressure profiles show large local variations across the bilayer for pure ceramide or any of the two-component mixtures. Close to the skin composition ratio, the lateral pressure fluctuations are greatly suppressed, the ceramide tails from the two leaflets interdigitate significantly, the depression in local density at the interleaflet region is lowered, and the bilayers have lowered elastic moduli. This indicates that the observed composition ratio in the stratum corneum lipid layer is responsible for both the good barrier properties and the stability of the lipid structure against mechanical stresses.

Coarse-grained simulations of flow-induced nucleation in semicrystalline polymers.

Abstract:After surveying the experimental evidence for concentration coupling in the shear banding of wormlike micellar surfactant systems, we present flow phase diagrams spanned by shear stress Σ (or strain rate ) and concentration, calculated within the two-fluid, non-local Johnson-Segalman (d-JS-φ) model. We also give results for the macroscopic flow curves Σ(¯,¯φ) for a range of (average) concentrations ¯φ. For any concentration that is high enough to give shear banding, the flow curve shows the usual non-analytic kink at the onset of banding, followed by a coexistence “plateau” that slopes upwards, dΣ/d¯ > 0. As the concentration is reduced, the width of the coexistence regime diminishes and eventually terminates at a non-equilibrium critical point [Σc,¯φc,¯c]. We outline the way in which the flow phase diagram can be reconstructed from a family of such flow curves, Σ(¯,¯φ), measured for several different values of ¯φ. This reconstruction could be used to check new measurements of concentration differences between the coexisting bands. Our d-JS-φ model contains two different spatial gradient terms that describe the interface between the shear bands. The first is in the viscoelastic constitutive equation, with a characteristic (mesh) length l. The second is in the (generalised) Cahn-Hilliard equation, with the characteristic length ξ for equilibrium concentration-fluctuations. We show that the phase diagrams (and so also the flow curves) depend on the ratio r ≡ l /ξ, with loss of unique state selection at r = 0. We also give results for the full shear-banded profiles, and study the divergence of the interfacial width (relative to l and ξ) at the critical point.