Spider Silk-CBD-Cellulose Nanocrystal Composites: Mechanism of Assembly

The fabrication of cellulose-spider silk bio-nanocomposites comprised of cellulose nanocrystals (CNCs) and recombinant spider silk protein fused to a cellulose binding domain (CBD) is described. Silk-CBD successfully binds cellulose, and unlike recombinant silk alone, silk-CBD self-assembles into microfibrils even in the absence of CNCs. Silk-CBD-CNC composite sponges and films show changes in internal structure and CNC alignment related to the addition of silk-CBD. The silk-CBD sponges exhibit improved thermal and structural characteristics in comparison to control recombinant spider silk sponges. The glass transition temperature (Tg) of the silk-CBD sponge was higher than the control silk sponge and similar to native dragline spider silk fibers. Gel filtration analysis, dynamic light scattering (DLS), small angle X-ray scattering (SAXS) and cryo-transmission electron microscopy (TEM) indicated that silk-CBD, but not the recombinant silk control, formed a nematic liquid crystalline phase similar to that observed in native spider silk during the silk spinning process. Silk-CBD microfibrils spontaneously formed in solution upon ultrasonication. We suggest a model for silk-CBD assembly that implicates CBD in the central role of driving the dimerization of spider silk monomers, a process essential to the molecular assembly of spider-silk nanofibers and silk-CNC composites.     

Hydrothermal degradation of adsorbed sulfur mustard on activated carbon

Thermal and hydrothermal degradations of adsorbed sulfur mustard (HD) on activated carbon particles from a chemical protective over-garment were studied. Carbon loaded with 5 wt.% HD was heated in a closed reactor at temperatures up to 160 °C for 0.5–6 h and analyzed by solid-state ¹³C MAS NMR. On dry carbon at room temperature, HD was stable for months. On a thoroughly pre-wetted carbon, adsorbed HD partially degraded to thiodiglycol (TDG) and TDG-sulfoxide (TDG-SO) within 2–3 months. Heating dry HD-loaded carbon to 160 °C caused partial degradation within 4 h to 1,4-thioxane, along with 1,4-dithiane and vinyl sulfides. Complete degradation within 2.5 h to the same products occurred upon hydrothermal treatment of the HD-loaded carbon, using a water/carbon ratio of 0.3:1. With higher water/carbon ratios of 0.6:1–5:1 at temperatures of 120 °C and above, adsorbed HD hydrolyzed rapidly within 0.5 h. The latter reaction led to the formation of TDG concurrent with either thioxane (at 160 °C) or TDG-SO and TDG-dimer (at 120 °C). The mechanisms of the observed degradation processes are discussed.     

Iron as an Oxygen Tracer at the Aluminum-Alumina Interface

During wetting experiments of pure aluminum on the (0001) plane of sapphire, an aluminum sample was unintentionally contaminated with 31 atoms/parts per million of iron. Transmission electron microscopy investigations of the sample after cooling showed the formation of FeAlO₃ at the aluminum-Al₂O₃ interface. Formation of FeAlO₃ confirms the existence of a high oxygen activity at the liquid aluminum-sapphire interface, which is considered to be the reason for the strong adhesion between aluminum and Al₂O₃. A low indexed orientation relationship between FeAlO₃ and Al₂O₃ was determined, where [22¯1]_FeAlO3‖ [11¯00]_Al2O₃ and (110)_FeAlO3‖ (0001)_Al2O₃.     

Production of Periclase-Carbon Refractories at Semiluki Refractory Plant

The technology and commercial production of periclase-carbon articles with a regular grain composition from a raw material with unstable grain size are described. A comparative study of casting, elemental, and crucible graphite as the basic carbon component has shown that the best commercial properties are provided by the use of crucible graphite. Tests of periclase-carbon refractories without metallic aluminum and with various contents of aluminum have shown the possibility of a differentiated approach to the use of the antioxidant with allowance for the specific service conditions of the lining.     

Natural-based polymers for antibacterial treatment of absorbent materials

In this study, polypropylene (PP) nonwoven fabric which can be used as topsheet layer of an absorbent hygienic product was modified by natural based antibacterial agents. Antibacterial herbal agents (cinnamaldehyde, geraniol, phenylethyl alcohol) were sprayed by ethanol or applied by means of polylactic acid (PLA) and polycyclohexene oxide (PCHO) based polymers prepared by three different chemical methods. Characterization of synthesized materials was conducted via thermogravimetric analysis (TGA), differential thermal analysis (DTA), and scanning electron microscopy–energy dispersive X–ray spectroscopy (SEM-EDX). Besides characterization, antibacterial and pH buffering performances of antibacterial polymers alone and on PP fabric were tested by antibacterial and pH tests. Effects of antibacterial treatments on air permeability and absorption period of nonwoven fabrics were also analyzed. According to the results, biopolymers changed the thermal stability of PP nonwoven fabric. Antibacterial performances can be ranked as cinnamaldehyde, geraniol, and phenylethyl alcohol from the best. Besides a slight decrease about liquid absorption performance, all of the treated topsheet fabrics are sufficient for an absorbent hygienic product. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48302.     

Structure of the Equilibrated Ni(111)‐YSZ(111) Solid–Solid Interface

Solid‐state dewetting of continuous Ni films deposited on the (111) surface of yttrium‐stabilized zirconia (YSZ) was used to produce equilibrated Ni particles, and the solid–solid interface structure was determined using aberration‐corrected transmission electron microscopy. The ~150 nm thick Ni films were annealed at 1350°C in Ar + H₂ (99.9999%) at a partial pressure of oxygen of 10^?20 atm for 6 h. Transmission electron microscopy of equilibrated particles, which was conducted to analyze the structure at the interface, revealed that despite the 31% lattice mismatch between Ni and YSZ, the interface is semicoherent and a two‐dimensional network of misfit dislocations was identified.     

Carnivore Attractant or Plant Elicitor? Multifunctional Roles of Methyl Salicylate Lures in Tomato Defense

Synthetic plant volatile lures attract natural enemies, but may have non-target effects due to the multifunctional nature of volatile signals. For example, methyl salicylate (MeSA) is used to attract predators, yet also serves as a signaling hormone involved in plant pathogen defense. We investigated the consequences of deploying MeSA lures to attract predators for tomato (Solanum lycopersicum) defense against herbivores. To understand the spatial distribution of the lure’s effect, we exposed tomatoes in the field to MeSA along a linear distance gradient and induced defenses by simulating feeding by hornworm caterpillars in a fully crossed factorial design (+/? MeSA, +/? herbivory). Subsequently, we analyzed activity of several defensive proteins (protease inhibitors, polyphenol oxidase, peroxidase), development of hornworm larvae (Manduca sexta), growth of fungal pathogens (Cladosporium and Alternaria), and attractiveness to herbivores and predators. Overall, MeSA-exposed plants were more resistant to both insects and pathogens. Secondary pathogen infection was reduced by 25% in MeSA exposed plants, possibly due to elevated polyphenol oxidase activity. Interestingly, we found that lures affected plant pathogen defenses equivalently across all distances (up to 4 m away) indicating that horizontal diffusion of a synthetic volatile may be greater than previously assumed. While thrips avoided colonizing hornworm– damaged tomato plants, this induced resistance was not observed upon pre-exposure to MeSA, suggesting that MeSA suppresses the repellant effect induced by herbivory. Thus, using MeSA lures in biological control may inadvertently protect crops from pathogens, but has mixed effects on plant resistance to insect herbivores.     

The combined influence of Mg and Ca on microstructural evolution of alumina

The solubility limits of Ca and Mg co-doped in alumina at 1600°C were determined by equilibrating alumina saturated with Ca and Mg. This resulted in the formation of MgAl₂O₄ (Mg spinel), CaO·6Al₂O₃ (CA6), Ca₂Mg₂Al₂₈O₄₆ (CAM-II), and alumina grains saturated with Mg and Ca. Under these conditions, the amount of Ca and Mg in the alumina grains represents the solubility limits. The solubility limits were measured using a fully standardized wavelength dispersive spectrometer mounted on a scanning electron microscope. In the co-doped state, the solubility limit of Ca in alumina was 32 ± 13 ppm, and the solubility limit of Mg in alumina was 210 ± 43 ppm. The presence of Ca results in an increase of the solubility limit of Mg in alumina from 132 to 210 ppm, suggesting that the increased Mg in solution results in more Mg excess at the alumina grain boundaries, thus contributing to a decreased grain-boundary mobility by solute-drag.     

Characterization and determination of swelling and diffusion characteristics of poly(n‐vinyl‐2‐pyrrolidone) hydrogels in water

Hydrogels in the form of rods with varying crosslink densities and three‐dimensional network structures were prepared from Poly(N‐vinyl‐2‐pyrrolidone) (PVP)/water and PVP/water/persulfate systems by irradiation with γ rays at ambient temperature. Average molecular weights between crosslinks, percent swelling, swelling equilibrium values, diffusion/swelling characteristics (i.e., the structure of network constant, the type of diffusion, the initial swelling rate, swelling rate constant), and equilibrium water content were evaluated for both hydrogel systems. Water diffusion to the hydrogel is a non‐Fickian type diffusion and diffusion coefficients vary from 6.56 × 10⁻⁷ to 2.51 × 10⁻⁷cm²min⁻¹ for PVP and 6.09 × 10⁻⁷ to 2.14 × 10⁻⁷ cm²min⁻¹ for PVP/persulfate hydrogel systems. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 994–1000, 2000     

Morphological and dielectric properties of barium chloride‐filled poly(vinylidene fluoride) films

Morphological characteristics of poly(vinylidene fluoride) (PVDF) films, filled with mass fractions (w ≤ 20%) of Barium Chloride (BaCl₂), were investigated by X‐ray diffraction (XRD), Fourier transform infrared (FTIR) absorption spectra and differential scanning calorimetry (DSC) measurements. The dielectric properties of films were measured from 250 Hz to 1 MHz range between 100 and 400 K as a function of frequency and temperature. Spectroscopic data revealed that the filled and unfilled films include α‐, β‐, and γ‐crystalline phases. By a 20% filling, 73% increase was obtained in the total degree of crystallinity. Since the BaCl₂ formed fluorine bridges over the chain segments on the crystal lamellar surface, the γ‐crystalline phase decreased, whereas the total degree of crystallinity increased. Dielectric measurements showed that maximum of the dielectric loss factor belonging to β‐relaxation transition decreased linearly with filling level. The filling process did not have any effect on the real dielectric constant till α‐relaxation transition region. However, in the α‐relaxation transition region, it was determined that the real dielectric constant increased linearly with filling level. POLYM. COMPOS., 31:1782–1789, 2010. © 2010 Society of Plastics Engineers.