Reversibly Sticking Metals and Graphite to Hydrogels and Tissues.

We have discovered that hard, electrical conductors (e.g., metals or graphite) can be adhered to soft, aqueous materials (e.g., hydrogels, fruit, or animal tissue) without the use of an adhesive. The adhesion is induced by a low DC electric field. As an example, when 5 V DC is applied to graphite slabs spanning a tall cylindrical gel of acrylamide (AAm), a strong adhesion develops between the anode (+) and the gel in about 3 min. This adhesion endures after the field is removed, and we term it as hard-soft electroadhesion or EA[HS]. Depending on the material, adhesion occurs at the anode (+), cathode (-), or both electrodes. In many cases, EA[HS] can be reversed by reapplying the field with reversed polarity. Adhesion via EA[HS] to AAm gels follows the electrochemical series: e.g., it occurs with copper, lead, and tin but not nickel, iron, or zinc. We show that EA[HS] arises via electrochemical reactions that generate chemical bonds between the electrode and the polymers in the gel. EA[HS] can create new hybrid materials, thus enabling applications in robotics, energy storage, and biomedical implants. Interestingly, EA[HS] can even be achieved underwater, where typical adhesives cannot be used.

A Smart Skin for Hydrogels That Enables Switchable Solute Release.

Many applications of hydrogels rely on their ability to deliver encapsulated solutes, such as drugs; however, small hydrophilic solutes rapidly leak out of gels by diffusion. A need exists for a way to regulate solute release out of gels─to ensure zero release until a desired time (the OFF state) and thereafter for the release to be switched ON at a high rate. This should ideally be a repeatable switch; i.e., the gel should be cyclable repeatedly between the ON and OFF states. Such perfect, cyclical ON-OFF release of solutes from gels is demonstrated for the first time through a "smart skin" that is synthesized rapidly (in ∼10 min) around an entire gel. The thin (∼100 µm) and transparent polymer skin is endowed with redox-responsive properties through the use of urethane and acrylate monomers, one of which contains a thioether group. Initially, the skin is hydrophobic (water contact angle 102°), and it completely prevents hydrophilic solutes from leaking out of the gel. When contacted with oxidants such as hydrogen peroxide (H2O2), the thioethers are converted to sulfoxides, making the skin hydrophilic (water contact angle 42°) and thereby turning ON the release of solutes. Conversely, solute release can be turned OFF subsequently by adding a reducing agent such as vitamin C that reverts the sulfoxides to thioethers and thus returns the skin to its hydrophobic state. The release rate in the ON state can be tuned via the skin thickness as well as the oxidant concentration. The ability to regulate solute delivery from gels using smart skins is likely to prove significant in areas ranging from separations to agriculture and drug delivery.

Chemically Fueled Dissipative Cross-Linking of Protein Hydrogels Mediated by Protein Unfolding.

Cells assemble dynamic protein-based nanostructures far from equilibrium, such as microtubules, in a process referred to as dissipative assembly. Synthetic analogues have utilized chemical fuels and reaction networks to form transient hydrogels and molecular assemblies from small molecule or synthetic polymer building blocks. Here, we demonstrate dissipative cross-linking of transient protein hydrogels using a redox cycle, which exhibit protein unfolding-dependent lifetimes and mechanical properties. Fast oxidation of cysteine groups on bovine serum albumin by hydrogen peroxide, the chemical fuel, formed transient hydrogels with disulfide bond cross-links that degraded over hours by a slow reductive back reaction. Interestingly, despite increased cross-linking, the hydrogel lifetime decreased as a function of increasing denaturant concentration. Experiments showed that the solvent-accessible cysteine concentration increased with increasing denaturant concentration due to unfolding of secondary structures. The increased cysteine concentration consumed more fuel, which led to less direction oxidation of the reducing agent and affected a shorter hydrogel lifetime. Increased hydrogel stiffness, disulfide cross-linking density, and decreased oxidation of redox-sensitive fluorescent probes at a high denaturant concentration provided evidence supporting the unveiling of additional cysteine cross-linking sites and more rapid consumption of hydrogen peroxide at higher denaturant concentrations. Taken together, the results indicate that the protein secondary structure mediated the transient hydrogel lifetime and mechanical properties by mediating the redox reactions, a feature unique to biomacromolecules that exhibit a higher order structure. While prior works have focused on the effects of the fuel concentration on dissipative assembly of non-biological molecules, this work demonstrates that the protein structure, even in nearly fully denatured proteins, can exert similar control over reaction kinetics, lifetime, and resulting mechanical properties of transient hydrogels.

Spontaneous Formation of Stable Vesicles and Vesicle Gels in Polar Organic Solvents.

The self-assembly of lipids into nanoscale vesicles (liposomes) is routinely accomplished in water. However, reports of similar vesicles in polar organic solvents like glycerol, formamide, and ethylene glycol (EG) are scarce. Here, we demonstrate the formation of nanoscale vesicles in glycerol, formamide, and EG using the common phospholipid lecithin (derived from soy). The samples we study are simple binary mixtures of lecithin and the solvent, with no additional cosurfactants or salt. Lecithin dissolves readily in the solvents and spontaneously gives rise to viscous fluids at low lipid concentrations (∼2-4%), with structures ∼200 nm detected by dynamic light scattering. At higher concentrations (>10%), lecithin forms clear gels that are strongly birefringent at rest. Dynamic rheology confirms the elastic response of gels, with their elastic modulus being ∼20 Pa at ∼10% lipid. Images from cryo-scanning electron microscopy (cryo-SEM) indicate that concentrated samples are "vesicle gels," where multilamellar vesicles (MLVs, also called "onions"), with diameters between 50 and 600 nm, are close-packed across the sample volume. This structure can explain both the elastic rheology as well as the static birefringence of the samples. The discovery of vesicles and vesicle gels in polar solvents widens the scope of systems that can be created by self-assembly. Interestingly, it is much easier to form vesicles in polar solvents than in water, and the former are stable indefinitely, whereas the latter tend to aggregate or coalesce over time. The stability is attributed to refractive index-matching between lipid bilayers and the solvents, i.e., these vesicles are relatively "invisible" and thus experience only weak attractions. The ability to use lipids (which are "green" or eco-friendly molecules derived from renewable natural sources) to thicken and form gels in polar solvents could also prove useful in a variety of areas, including cosmetics, pharmaceuticals, and lubricants.

Tensile Testing of Aged Flexible Unidirectional Composite Laminates for Body Armor.

Flexible Unidirectional (UD) composite laminates are commonly being used for ballistic-resistant body armor. These laminates comprise UD layers, each constructed by laminating thin layers of high-performance fibers held in place using very low modulus binder resins, with the fibers in each layer oriented parallel to each other. As these materials are used in body armor, it is important to investigate their long-term reliability, particularly with regards to exposure to temperature and humidity as these are known causes of degradation in other commonly used body armor materials. This work investigates the tensile behavior of a poly(p-phenylene terephthalamide), or PPTA flexible UD laminate aged for up to 150 d at accelerated conditions of 70 °C and 76 % relative humidity (RH). Tests were performed at three different crosshead displacement rates and three different gauge lengths. The effect of ageing on the mechanical properties of the material resulted in less than 10 % degradation in tensile strength, with a more significant reduction in longer specimens when tested at slower rates.

Cutting Procedures, Tensile Testing, and Ageing of Flexible Unidirectional Composite Laminates.

Many body armor designs incorporate unidirectional (UD) laminates. UD laminates are constructed of thin (<0.05 mm) layers of high-performance yarns, where the yarns in each layer are oriented parallel to each other and held in place using binder resins and thin polymer films. The armor is constructed by stacking the unidirectional layers in different orientations. To date, only very preliminary work has been performed to characterize the ageing of the binder resins used in unidirectional laminates and the effects on their performance. For example, during the development of the conditioning protocol used in the National Institute of Justice Standard-0101.06, UD laminates showed visual signs of delamination and reductions in V50, which is the velocity at which half of the projectiles are expected to perforate the armor, after ageing. A better understanding of the material property changes in UD laminates is necessary to comprehend the long-term performance of armors constructed from these materials. There are no current standards recommended for mechanically interrogating unidirectional (UD) laminate materials. This study explores methods and best practices for accurately testing the mechanical properties of these materials and proposes a new test methodology for these materials. Best practices for ageing these materials are also described.

Multiscale Polymer Dynamics in Hierarchical Carbon Nanotube Grafted Glass Fiber Reinforced Composites.

Carbon nanotube (CNT) grafted glass fiber reinforced epoxy nanocomposites (GFRP) present a range of stiffnesses (MPa to GPa) and length scales (µm to nm) at the fiber-matrix interface. The contribution of functionalized CNT networks to the local and bulk polymer dynamics is studied here by using a combination of torsion dynamical mechanical thermal analysis (DMTA), positron annihilation lifetime spectroscopy (PALS), and neutron scattering (NS) measurements. DMTA measurements highlight a reduction in the storage modulus (G') in the rubbery region and an asymmetric broadening of the loss modulus (G″) peak in the α-transition region. NS measurements show a suppressed hydrogen mean-square displacement (MSD) in the presence of glass fibers but a higher hydrogen MSD after grafting functionalized CNTs onto fiber surfaces. PALS measurements show greater free volume characteristics in the presence of the functionalized CNT modified composites, supporting the view that these interface layers increase polymer mobility. While NS and DMTA are sensitive to different modes of chain dynamics, the localization of functionalized nanotubes at the fiber interface is found to affect the distribution of polymer relaxation modes without significantly altering the thermally activated relaxation processes.