The morphology of decorated amyloid fibers is controlled by the conformation and position of the displayed protein.

Self-assembled structures capable of mediating electron transfer are an attractive scientific and technological goal. Therefore, systematic variants of SH3-Cytochrome b(562) fusion proteins were designed to make amyloid fibers displaying heme-b(562) electron transfer complexes. TEM and AFM data show that fiber morphology responds systematically to placement of b(562) within the fusion proteins. UV-vis spectroscopy shows that, for the fusion proteins under test, only half the fiber-borne b(562) binds heme with high affinity. Cofactor binding also improves the AFM imaging properties and changes the fiber morphology through changes in cytochrome conformation. Systematic observations and measurements of fiber geometry suggest that longitudinal registry of subfilaments within the fiber, mediated by the interaction and conformation of the displayed proteins and their interaction with surfaces, gives rise to the observed morphologies, including defects and kinks. Of most interest is the role of small molecule modulation of fiber structure and mechanical stability. A minimum complexity model is proposed to capture and explain the fiber morphology in the light of these results. Understanding the complex interplay between these factors will enable a fiber design that supports longitudinal electron transfer.

Fabrication and electromechanical characterization of near-field electrospun composite fibers.

We report the use of near-field electrospinning (NFES) as a route to fabricate composite electrodes. Electrodes made of composite fibers of multi-walled carbon nanotubes in polyethylene oxide (PEO) are formed via liquid deposition, with precise control over their configuration. The electromechanical properties of free-standing fibers and fibers deposited on elastic substrates are studied in detail. In particular, we examine the elastic deformation limit of the resulting free-standing fibers and find, similarly to bulk PEO composites, that the plastic deformation onset is below 2% of tensile strain. In comparison, the apparent deformation limit is much improved when the fibers are integrated onto a stretchable, elastic substrate. It is hoped that the NFES fabrication protocol presented here can provide a platform to direct-write polymeric electrodes, and to integrate both stiff and soft electrodes onto a variety of polymeric substrates.

Accelerated and real-time creep and creep-rupture results for aramid fibers

This article presents results from conventional creep tests (CCT) and two accelerated test methods (the stepped isothermal method (SIM) and the stepped isostress method (SSM)) to determine the creep and creep-rupture behavior of two different aramid fibers, Kevlar 49 and Technora. CCT are regarded as the true behavior of the yarn, but they are impractical for long-term use where failures are expected only after many years. All the tests were carried out on the same batches of yarns, and using the same clamping arrangements, so the tests should be directly comparable. For both materials, SIM testing gives good agreement with CCT and gave stress-rupture lifetimes that followed the same trend. However, there was significant variation for SSM testing, especially when testing Technora fibers. The results indicate that Kevlar has a creep strain capacity that is almost independent of stress, whereas Technora shows a creep strain capacity that depends on stress. Its creep strain capacity is approximately two to three times that of Kevlar 49. The accelerated test methods give indirect estimates for the activation energy and the activation volume of the fibers. The activation energy for Technora is about 20% higher than that for Kevlar, meaning that it is less sensitive to the effects of increasing temperature. The activation volume for both materials was similar, and in both cases, stress dependent. Copyright © 2012 Wiley Periodicals, Inc.

Creep and strength retention of aramid fibers

Creep tests at ambient conditions have been carried out on Kevlar 49 and Technora yarns covering a wide stress spectrum (10-70% average breaking load) for a long period of time (up to a year). The results confirm that Kevlar 49 and Technora yarns show a nonlinear behavior at stresses below 40% of the breaking load and a linear behavior at stresses above 40%. The strength retention following creep for Kevlar 49 and Technora has also been examined. The results show a significant difference in the behavior of the two materials. Kevlar 49 appears to lose strength almost linearly with time, while Technora seems to lose strength much more rapidly. These results would have significant implications for design. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012 Copyright © 2012 Wiley Periodicals, Inc.

Fibers with integrated mechanochemical switches: minimalistic design principles derived from fibronectin.

Inspired by molecular mechanisms that cells exploit to sense mechanical forces and convert them into biochemical signals, chemists dream of designing mechanochemical switches integrated into materials. Using the adhesion protein fibronectin, whose multiple repeats essentially display distinct molecular recognition motifs, we derived a computational model to explain how minimalistic designs of repeats translate into the mechanical characteristics of their fibrillar assemblies. The hierarchy of repeat-unfolding within fibrils is controlled not only by their relative mechanical stabilities, as found for single molecules, but also by the strength of cryptic interactions between adjacent molecules that become activated by stretching. The force-induced exposure of cryptic sites furthermore regulates the nonlinearity of stress-strain curves, the strain at which such fibers break, and the refolding kinetics and fraction of misfolded repeats. Gaining such computational insights at the mesoscale is important because translating protein-based concepts into novel polymer designs has proven difficult.