Matthew B. Dickerson

Chemical reduction of three-dimensional silica micro-assemblies into microporous silicon replicas

The carbothermal reduction of silica into silicon requires the use of temperatures well above the silicon melting point (≥2,000 °C). Solid silicon has recently been generated directly from silica at much lower temperatures (≤850 °C) via electrochemical reduction in molten salts. However, the silicon products of such electrochemical reduction did not retain the microscale morphology of the starting silica reactants. Here we demonstrate a low-temperature (650 °C) magnesiothermic reduction process for converting three-dimensional nanostructured silica micro-assemblies into microporous nanocrystalline silicon replicas. The intricate nanostructured silica microshells (frustules) of diatoms (unicellular algae) were converted into co-continuous, nanocrystalline mixtures of silicon and magnesia by reaction with magnesium gas. Selective magnesia dissolution then yielded an interconnected network of silicon nanocrystals that retained the starting three-dimensional frustule morphology. The silicon replicas possessed a high specific surface area (>500 m2 g-1), and contained a significant population of micropores (≤20 Å). The silicon replicas were photoluminescent, and exhibited rapid changes in impedance upon exposure to gaseous nitric oxide (suggesting a possible application in microscale gas sensing). This process enables the syntheses of microporous nanocrystalline silicon micro-assemblies with multifarious three-dimensional shapes inherited from biological or synthetic silica templates for sensor, electronic, optical or biomedical applications.

Identification of peptides capable of inducing the formation of titania but not silica via a subtractive bacteriophage display approach

A “subtractive” bacteriophage display biopanning approach has been used to identify 12-mer peptides that are capable of binding selectively to, and inducing the precipitation of, titania but not silica. Unlike the conventional bacteriophage display procedure, this approach consists of two selection steps: i) removal of phage particles containing silica-binding peptides from the phage library (the subtractive step), and then ii) isolation of phage particles bearing peptides that bind strongly to titania. While prior phage display biopanning with silica and titania targets has led to the isolation of polycationic peptides enriched in basic residues, the subtractive biopanning process yielded several acidic peptides enriched in hydroxyl-bearing residues. These peptides were found to induce the precipitation of titania, but not silica, from aqueous precursor solutions at pH 3–8. To our knowledge, this is the first demonstration that a subtractive bacteriophage biopanning process may be used to identify specific peptides possessing the ability to induce the formation of one oxide while lacking the ability to form a second, chemically similar oxide.

Stabilization of organophosphorus hydrolase by entrapment in silk fibroin: formation of a robust enzymatic material suitable for surface coatings.

Organophosphates are some of the most acutely toxic compounds synthesized on an industrial scale, and organophosphorus hydrolase (OPH) has the ability to hydrolyze and inactivate a number of these chemicals. However, OPH activity is vulnerable to harsh environmental conditions that would accompany its practical utility in the field; a limitation that can also be extended to conditions required for incorporation of OPH into useful materials. Here we present evidence that entrapment of OPH in silk fibroin leads to stabilization of OPH activity under a variety of conditions that would otherwise reduce free enzyme activity, such as elevated temperature, UV light exposure and the presence of detergent. Silk fibroin entrapment of OPH also allowed for its dispersal into a polyurethane-based coating that retained organophosphate hydrolysis activity after formulation, application and drying. Together, the data presented here demonstrate the utility of silk fibroin entrapment for the protection of OPH activity under a variety of environmental conditions.

Incongruent reduction of tungsten carbide by a zirconium-copper melt

The reduction of tungsten carbide (WC) to elemental tungsten by reaction with a Zr-Cu melt was examined. Dense WC disks were immersed in a vertical orientation in molten Zr 2 Cu at 1150-1400 °C for 1.5-24 h. Continuous, adherent layers of W and ZrC formed at WC/melt interfaces. The rates of thickening of the W and ZrC product layers were examined as a function of reaction time and temperature and position along the vertical WC surface. Such kinetic data, along with microstructural analyses, indicate that the incongruent reduction of tungsten carbide is likely to be controlled by carbon diffusion through one or both of the product layers.

Keratin-based antimicrobial textiles, films, and nanofibers

The combination of appealing structural properties, biocompatibility, and the availability of renewable and inexpensive raw materials, make keratin-based materials attractive for a variety of applications. In this paper, we report on the antimicrobial functionalization of keratin-based materials, including wool cloth and regenerated cellulose/keratin composite films and nanofibers. The functionalization of these materials was accomplished utilizing a facile chlorination reaction that converts the nitrogen-bearing moieties of keratin into halamine compounds. Halamine-charged wool cloth exhibited rapid and potent bactericidal activity against several species of bacteria and induced up to a 5.3 log (i.e., 99.9995%) reduction in the colony forming units of Bacillus thuringiensis spores within 10 min. Keratin-containing composites were prepared by the spin coating and coaxial electrospinning of extracted/oxidized alpha-keratin and cellulose acetate (CA) solubilized in formic acid, followed by CA deacetylation. Regenerated cellulose/keratin materials chlorinated to display halamines were also effective in killing Escherichia coli and Staphylococcus aureus bacteria. Electrospun core/shell nanofibers engineered to maximize keratin-Cl surface area displayed higher activity against S. aureus than films composed of the same materials. The halamine-based antimicrobial functionalization methods demonstrated for keratin-based materials in this paper are anticipated to translate to other protein biopolymers of interest to the biomaterials community.

Sporicidal/Bactericidal Textiles via the Chlorination of Silk

Bacterial spores, such as those of the Bacillus genus, are extremely resilient, being able to germinate into metabolically active cells after withstanding harsh environmental conditions or aggressive chemical treatments. The toughness of the bacterial spore in combination with the use of spores, such as those of Bacillus anthracis, as a biological warfare agent necessitates the development of new antimicrobial textiles. In this work, a route to the production of fabrics that kill bacterial spores and cells within minutes of exposure is described. Utilizing this facile process, unmodified silk cloth is reacted with a diluted bleach solution, rinsed with water, and dried. The chlorination of silk was explored under basic (pH 11) and slightly acidic (pH 5) conditions. Chloramine-silk textiles prepared in acidified bleach solutions were found to have superior breaking strength and higher oxidative Cl contents than those prepared under caustic conditions. Silk cloth chlorinated for ≥1 h at pH 5 was determined to induce >99.99996% reduction in the colony forming units of Escherichia coli, as well as Bacillus thuringiensis Al Hakam (B. anthracis simulant) spores and cells within 10 min of contact. The processing conditions presented for silk fabric in this study are highly expeditionary, allowing for the on-site production of protein-based antimicrobial materials from a variety of agriculturally produced feed-stocks.

Identification of peptides that promote the rapid precipitation of germania nanoparticle networks via use of a peptide display library

Peptides that promote the rapid, room-temperature precipitation of amorphous germania nanoparticle networks from solution have been identified via use of a combinatorial peptide display library.

Dielectric breakdown strength of regenerated silk fibroin films as a function of protein conformation.

Derived from Bombyx mori cocoons, regenerated silk fibroin (RSF) exhibits excellent biocompatibility, high toughness, and tailorable biodegradability. Additionally, RSF materials are flexible, optically clear, easily patterned with nanoscale features, and may be doped with a variety bioactive species. This unique combination of properties has led to increased interest in the use of RSF in sustainable and biocompatible electronic devices. In order to explore the applicability of this biopolymer to the development of future bioelectronics, the dielectric breakdown strength (Ebd) of RSF thin films was quantified as a function of protein conformation. The application of processing conditions that increased β-sheet content (as determined by FTIR analysis) and produced films in the silk II structure resulted in RSF materials with improved Ebd with values reaching up to 400 V/μm.

Rubber muscle actuation with pressurized CO2 from enzyme-catalyzed urea hydrolysis

A biologically inspired pneumatic pressure source was designed and sized to supply high pressure CO2(g) to power a rubber muscle actuator. The enzyme urease served to catalyze the hydrolysis of urea, producing CO2(g) that flowed into the actuator. The actuators power envelope was quantified by testing actuator response on a custom-built linear-motion rig. Reaction kinetics and available work density were determined by replacing the actuator with a double-action piston and measuring volumetric gas generation against a fixed pressure on the opposing piston. Under the conditions investigated, urease catalyzed the generation of up to 0.81 MPa (117 psi) of CO2(g) in the reactor headspace within 18 min, and the evolved gas produced a maximum work density of 0.65 J ml−1.

Power Response of a Muscle Actuator Driven by a Regenerative, Enzymatic Pressurization Mechanism

Inspired by the characteristics of biological muscles, rubber muscle actuators (RMAs) are lightweight and compliant structures that deliver high power/weight ratios and are currently under investigation for use in soft robotics, prosthetics, and specialized aircraft. RMA actuation is accomplished by inflating the structure’s air bladder, which results in the contraction of the muscle. In this proceedings paper, we describe the use of gaseous products from enzymatically-catalyzed reactions to pressurize and drive the motion of RMAs. Specifically, this paper details the power envelope of RMAs driven by the urease-catalyzed production of CO2, under dynamic loading conditions. The use of enzymatically catalyzed, gas-producing reactions is advantageous for powering RMAs, as these systems may be self-regulating and self-regenerating. Reaction design parameters for sizing the gas source to RMA power requirements and power envelope results are reported for gas-powered actuator dynamics tested on a linear motion test assembly. The power response to increasing loads reflects the partial pressure over the reaction slurry; therefore, the chemistry and reactor scale affect the entire structure’s efficiency. We outline the reactor space-time design constraints that facilitate a tailored power response for urease catalyzed gas generation sources.Copyright