Effects of sea water pH on marine mussel plaque maturation.

Marine mussel plaques are an exceptional model for wet adhesives. Despite advances in understanding their protein composition and strategies for molecular bonding, the process by which these soluble proteins are rapidly processed into load-bearing structures remains poorly understood. Here, we examine the effects of seawater pH on the time evolution of the internal microstructures in plaques harvested from Mytilus californianus. Experimentally, plaques deposited by mussels on glass and acrylic surfaces were collected immediately after foot retraction without plaque separation from the surface, placed into pH-adjusted artificial seawater for varying times, and characterized using scanning electron microscopy and tensile testing. We found a pH dependent transition from a liquid-like state to a porous solid within 30 min for pH ≥ 6.7; these plaques are load-bearing. By contrast, samples maintained at pH 3.0 showed no porosity and no measurable strength. Interestingly, we found cuticle development within 15 min regardless of pH, suggesting that cuticle formation occurs prior to pore assembly. Our results suggest that sea water infusion after deposition by and disengagement of the foot is critical to the rapid formation of internal structures, which in turn plays an important role in the plaques' mechanical performance.

Evaluation of Eight Essential Oils for Postharvest Control of Aspergillus carbonarius in Grapes.

ABSTRACT: A range of fungal species are associated with postharvest spoilage of grapes. However, Aspergillus carbonarius is the primary fungus responsible for the contamination of grapes with ochratoxin A, a mycotoxin causing several confirmed negative health effects in humans and animals. Aiming to find a method, safe for consumers, to prevent postharvest decay and ochratoxin A contamination of grapes, the potential use of essential oils as preservatives was investigated. Essential oils of Origanum dictamnus (dittany), Origanum onites (oregano), Origanum microphyllum (marjoram), Thymbra capitata (thyme), Satureja thymbra (savory), Rosmarinus officinalis (rosemary), Laurus nobilis (laurel), and Salvia officinalis (sage) were tested. The essential oil components were identified by gas chromatography-mass spectrometry analysis. A first evaluation of the effectiveness of essential oils was performed in vitro at a range of concentrations up to 300 µL L-1. Based on the results of the in vitro tests, the four most effective essential oils (O. dictamnus, O. onites, T. capitata, and S. thymbra) were tested on Sultana grapes during postharvest storage. The four essential oils tested, which had carvacrol and/or thymol as a common component, at a high concentration significantly reduced or even inhibited growth of the fungus in all treatments. As revealed from the results, the essential oils of O. dictamnus, O. onites, and S. thymbra were the most effective, causing total inhibition of the growth of the fungus with a minimum concentration of 100 µL L-1, followed by the essential oil of T. capitata, which showed total effectiveness with a minimum concentration of 200 µL L-1. Although essential oils of O. microphyllum, L. nobilis, S. officinalis, and R. officinalis had a significant effect on the growth of A. carbonarius, they failed to inhibit its growth at any of the concentrations tested.

Toughening elastomers using mussel-inspired iron-catechol complexes.

Materials often exhibit a trade-off between stiffness and extensibility; for example, strengthening elastomers by increasing their cross-link density leads to embrittlement and decreased toughness. Inspired by cuticles of marine mussel byssi, we circumvent this inherent trade-off by incorporating sacrificial, reversible iron-catechol cross-links into a dry, loosely cross-linked epoxy network. The iron-containing network exhibits two to three orders of magnitude increases in stiffness, tensile strength, and tensile toughness compared to its iron-free precursor while gaining recoverable hysteretic energy dissipation and maintaining its original extensibility. Compared to previous realizations of this chemistry in hydrogels, the dry nature of the network enables larger property enhancement owing to the cooperative effects of both the increased cross-link density given by the reversible iron-catecholate complexes and the chain-restricting ionomeric nanodomains that they form.

Influence of multi-cycle loading on the structure and mechanics of marine mussel plaques.

The proteinaceous byssal plaque-thread structures created by marine mussels exhibit extraordinary load-bearing capability. Although the nanoscopic protein interactions that support interfacial adhesion are increasingly understood, major mechanistic questions about how mussel plaques maintain toughness on supramolecular scales remain unanswered. This study explores the mechanical properties of whole mussel plaques subjected to repetitive loading cycles, with varied recovery times. Mechanical measurements were complemented with scanning electron microscopy to investigate strain-induced structural changes after yield. Multicyclic loading of plaques decreases their low-strain stiffness and introduces irreversible, strain-dependent plastic damage within the plaque microstructure. However, strain history does not compromise critical strength or maximum extension compared with plaques monotonically loaded to failure. These results suggest that a multiplicity of force transfer mechanisms between the thread and plaque-substrate interface allow the plaque-thread structure to accommodate a wide range of extensions as it continues to bear load. This improved understanding of the mussel system at micron-to-millimeter lengthscales offers strategies for including similar fail-safe mechanisms in the design of soft, tough and resilient synthetic structures.

Significant Performance Enhancement of Polymer Resins by Bioinspired Dynamic Bonding.

Marine mussels use catechol-rich interfacial mussel foot proteins (mfps) as primers that attach to mineral surfaces via hydrogen, metal coordination, electrostatic, ionic, or hydrophobic bonds, creating a secondary surface that promotes bonding to the bulk mfps. Inspired by this biological adhesive primer, it is shown that a ≈1 nm thick catecholic single-molecule priming layer increases the adhesion strength of crosslinked polymethacrylate resin on mineral surfaces by up to an order of magnitude when compared with conventional primers such as noncatecholic silane- and phosphate-based grafts. Molecular dynamics simulations confirm that catechol groups anchor to a variety of mineral surfaces and shed light on the binding mode of each molecule. Here, a ≈50% toughness enhancement is achieved in a stiff load-bearing polymer network, demonstrating the utility of mussel-inspired bonding for processing a wide range of polymeric interfaces, including structural, load-bearing materials.

The microscopic network structure of mussel (Mytilus) adhesive plaques.

Marine mussels of the genus Mytilus live in the hostile intertidal zone, attached to rocks, bio-fouled surfaces and each other via collagen-rich threads ending in adhesive pads, the plaques. Plaques adhere in salty, alkaline seawater, withstanding waves and tidal currents. Each plaque requires a force of several newtons to detach. Although the molecular composition of the plaques has been well studied, a complete understanding of supra-molecular plaque architecture and its role in maintaining adhesive strength remains elusive. Here, electron microscopy and neutron scattering studies of plaques harvested from Mytilus californianus and Mytilus galloprovincialis reveal a complex network structure reminiscent of structural foams. Two characteristic length scales are observed characterizing a dense meshwork (approx. 100 nm) with large interpenetrating pores (approx. 1 µm). The network withstands chemical denaturation, indicating significant cross-linking. Plaques formed at lower temperatures have finer network struts, from which we hypothesize a kinetically controlled formation mechanism. When mussels are induced to create plaques, the resulting structure lacks a well-defined network architecture, showcasing the importance of processing over self-assembly. Together, these new data provide essential insight into plaque structure and formation and set the foundation to understand the role of plaque structure in stress distribution and toughening in natural and biomimetic materials.

Dynamics of non-Brownian fiber suspensions under periodic shear.

We report experiments studying the dynamics of dense non-Brownian fiber suspensions subjected to periodic oscillatory shear. We find that periodic shear initially causes fibers to collide and to undergo irreversible diffusion. As time progresses, the fibers tend to orient in the vorticity direction while the number of collisions decreases. Ultimately, the system goes to one of two steady states: an absorbing steady state, where collisions cease and the fibers undergo reversible trajectories; an active state, where fibers continue to collide causing them to diffuse and undergo irreversible trajectories. Collisions between fibers can be characterized by an effective volume fraction Φ with a critical volume fraction Φc that separates absorbing from active (diffusing) steady states. The effective volume fraction Φ depends on the mean fiber orientation and thus decreases in time as fibers progressively orient under periodic shear. In the limit that the temporal evolution of Φ is slow compared to the activity relaxation time τ, all the data for all strain amplitudes and all concentrations can be scaled onto a single master curve with a functional dependence well-described by t(-ß/ν)R(e(-t)R), where tR is the rescaled time. As Φ â†’ Φc, τ diverges. Therefore, for experiments in which Φ(t) starts above Φc but goes to a steady state below Φc, departures from scaling are observed for Φ very near Φc. The critical exponents are measured to be ß = 0.84 ± 0.04 and ν = 1.1 ± 0.1, which is consistent with the Manna universality class for directed percolation.

Tunable silk: using microfluidics to fabricate silk fibers with controllable properties.

Despite widespread use of silk, it remains a significant challenge to fabricate fibers with properties similar to native silk. It has recently been recognized that the key to tuning silk fiber properties lies in controlling internal structure of assembled ß-sheets. We report an advance in the precise control of silk fiber formation with control of properties via microfluidic solution spinning. We use an experimental approach combined with modeling to accurately predict and independently tune fiber properties including Young's modulus and diameter to customize fibers. This is the first reported microfluidic approach capable of fabricating functional fibers with predictable properties and provides new insight into the structural transformations responsible for the unique properties of silk. Unlike bulk processes, our method facilitates the rapid and inexpensive fabrication of fibers from small volumes (50 µL) that can be characterized to investigate sequence-structure-property relationships to optimize recombinant silk technology to match and exceed natural silk properties.

Transverse alignment of fibers in a periodically sheared suspension: an absorbing phase transition with a slowly varying control parameter.

Shearing solutions of fibers or polymers tends to align fiber or polymers in the flow direction. Here, non-Brownian rods subjected to oscillatory shear align perpendicular to the flow while the system undergoes a nonequilibrium absorbing phase transition. The slow alignment of the fibers can drive the system through the critical point and thus promote the transition to an absorbing state. This picture is confirmed by a universal scaling relation that collapses the data with critical exponents that are consistent with conserved directed percolation.