Photochemistry of aqueous C₆₀ clusters: wavelength dependency and product characterization

To construct accurate risk assessment models for engineered nanomaterials, there is urgent need for information on the reactivity (or conversely, persistence) and transformation pathways of these materials in the natural environment. As an important step toward addressing this issue, we have characterized the products formed when aqueous C(60) clusters (nC(60)) are exposed to natural sunlight and also have assessed the wavelengths primarily responsible for phototransformation. Long-wavelength light (λ ≥ 400 nm) isolated from sunlight, was shown to be important in both the phototransformation of nC(60) and in the production of (1)O(2). The significance of visible light in mediating the phototransformation of nC(60) was supported by additional experiments with monochromatic light in which the apparent quantum yield at 436 nm (Φ(436 nm) = (2.08 ± 0.08) × 10(-5)) was comparable to that at 366 nm (Φ(366 nm) = (2.02 ± 0.07) × 10(-5)). LDI-TOF mass spectrometry indicated that most of the photoproducts formed after 947 h of irradiation in natural sunlight retain a 60 atom carbon structure. A combination of (13)C NMR analysis of (13)C-enriched nC(60), X-ray photoelectron spectroscopy and FTIR indicated that photoproducts have olefinic carbon atoms as well as a variety of oxygen-containing functional groups, including vinyl ether and carbonyl or carboxyl groups, whose presence destroys the native π-electron system of C(60). Thus, the photoreactivity of nC(60) in sunlight leads to the formation of water-soluble C(60) derivatives.     

Conversion of Extracted Oil Cake Fibers into Bioethanol Including DDGS,Canola, Sunflower,Sesame, Soy,and Peanut for Integrated Biodiesel Processing

We have come up with a novel, integrated approach for making biodiesel by in-house producion of ethanol after fermentation of hexane extracted edible oil cake fiber. In addition, we have demonstrated how ethanol could be manufactured from commonly available oil cakes (such as canola, sunflower, sesame, soy, peanut) and dried distiller’s grains with solubles (DDGS). The edible oil cakes and DDGS were hexane extracted, ammonia fiber expansion pretreated, enzymatically hydrolysed and fermented to produce ethanol. From all the oil cakes tested in this work, DDGS and peanut oil cake showed the most promising results giving more than 180 g of glucose/kg of oil cake. These two feedstock’s were hydrolyzed at 15% solids loading and fermented by a native strain of Pichia stipitis. Most sugars were consumed during the first 24 h, with no pronounced inhibition of P. stipitis by the degradation products in the hydrolysate. Xylose consumption was more effective for peanut cake hydrolyzate compared to DDGS.     

Potentials with small‐angle neutron scattering technique for understanding structure–property relation of 3D‐printed materials

Carbon fiber (CF)‐embedded acrylonitrile butadiene styrene polymer composites printed on the large‐scale printer at Oak Ridge National Laboratory were investigated by small‐angle neutron scattering to correlate the microstructure of the composites with their mechanical strength. The microstructure of the polymer domains and the alignment of CF were characterized across the interfaces between layers of the hot‐melt extruded material and were compared with CF‐free ABS. The small‐angle neutron scattering data show that the CF‐containing material displays strong anisotropic scatterings suggesting molecular alignment along the printing direction that is not present in the CF‐free ABS. Scattering data analysis across the interfacial layer revealed enhanced molecular alignment along the printing direction near the boundaries and inhomogeneous size distribution of polymer domains upon the addition of CF. We attribute the compromised strength across interfacial layers from CF‐containing material to this inhomogeneous size distribution which prevents effective lateral interaction between layers. POLYM. ENG. SCI., 59:E65–E70, 2019. © 2018 Society of Plastics Engineers     

Buckminsterfullerene's (C60) octanol-water partition coefficient (Kow) and aqueous solubility

To assess the risk and fate of fullerene C60 in the environment, its water solubility and partition coefficients in various systems are useful. In this study, the log Kow of C60 was measured to be 6.67, and the toluene-water partition coefficient was measured at log Ktw = 8.44. From these values and the respective solubilities of C60 in water-saturated octanol and water-saturated toluene, C60's aqueous solubility was calculated at 7.96 ng/L(1.11 x 10(-11) M) for the organic solvent-saturated aqueous phase. Additionally, the solubility of C60 was measured in mixtures of ethanol-water and tetrahydrofuran-water and modeled with Wohl's equation to confirm the accuracy of the calculated solubility value. Results of a generator column experiment strongly support the hypothesis that clusters form at aqueous concentrations below or near this calculated solubility. The Kow value is compared to those of other hydrophobic organic compounds, and bioconcentration factors for C60 were estimated on the basis of Kow.     

Solubility of C60 in solvent mixtures

The potential large-scale production of fullerene C60 and its widespread use in consumer products may translate into occupational and public exposure and in long-term environmental exposure. To assess the risk and fate of C60 in the environment, it is important to understand its solvate formation in common industrial solvents as the solvates may affect various properties of C60 including reactivity and toxicity, particularly when solvates occur in C60 clusters. In this study, the solubility measurements in mixed solvent system can provide useful information about solvate formation. The solubility of C60 was measured in pure toluene, tetrahydrofuran, ethanol, and acetonitrile to be 3000, 11, 1.4, and 0.04 mg/L, respectively. Additionally, the solubility of C60 was measured in mixtures of toluene-acetonitrile, toluene-ethanol, toluene-tetrahydrofuran, and acetonitrile-tetrahydrofuran. The solubility data were modeled with some accuracy using Wohl's equation. The estimated crystal energy term for C60 in tetrahydrofuran was different than that in the other solvents, indicating that the C60 solid phase in equilibrium with tetrahydrofuran solution may be a solvated crystal.     

Effects of red-wine grape pomace on the quality and sensory attributes of beef hamburger patty

This study was conducted to evaluate the effect of red-wine grape pomaces on the quality and sensory attributes of beef hamburger patties. Both phenolic content and antioxidant activity were assessed using Syrah, Merlot and Cabernet Sauvignon pomaces. Following the assessment, hamburger patties were prepared with Merlot pomace at 0%, 2% and 4% for the patty quality and sensory attributes. Grape seeds possessed significantly higher phenolics and antioxidant activities over the seedless pomace (P < 0.05), whereas no significant difference was found for phenolics and antioxidant activities within the seeds and seedless pomaces. The patty pH decreased as the pomace was added for 2% and 4%. Colour values (L*, a* and b*) of patties lowered as the pomace was added. Allo-Kramer shear force and hardness values increased while cooking yield decreased (P < 0.05) with the addition of pomace. No significant difference between control and Merlot patties was found for flavour, juiciness and colour, whereas lower sensory attributes were observed for texture, taste and overall acceptability. It is observed that the addition of fermented red-wine grape pomace provides hamburger patties with health promoting factors such as antioxidant and other functional components, but it also provided darker, sourer and lower cooking yield.     

Light-Responsive Colloidal Crystals Engineered with DNA

A novel method for synthesizing and photopatterning colloidal crystals via light-responsive DNA is developed. These crystals are composed of 10–30 nm gold nanoparticles interconnected with azobenzene-modified DNA strands. The photoisomerization of the azobenzene molecules leads to reversible assembly and disassembly of the base-centered cubic (bcc) and face-centered cubic (fcc) crystalline nanoparticle lattices. In addition, UV light is used as a trigger to selectively remove nanoparticles on centimeter-scale thin films of colloidal crystals, allowing them to be photopatterned into preconceived shapes. The design of the azobenzene-modified linking DNA is critical and involves complementary strands, with azobenzene moieties deliberately staggered between the bases that define the complementary code. This results in a tunable wavelength-dependent melting temperature (T_m) window (4.5–15 °C) and one suitable for affecting the desired transformations. In addition to the isomeric state of the azobenzene groups, the size of the particles can be used to modulate the T_m window over which these structures are light-responsive.     

A methodology for predicting and comparing the full‐scale fire performance of similar materials based on small‐scale testing

Reconstructive fire testing is an important tool used by fire investigators to determine the cause, origin, and progression of a particular fire. Accurate reconstruction of the fire requires the laboratory structure to be outfitted with materials that, in terms of contribution to fire growth, perform similarly to the original materials found at the fire scene. Therefore, a procedure was developed to enable fire investigators to select these replacement materials on the basis of a quantitative assessment of their relative fire performance. This procedure consists of gram‐scale and/or milligram‐scale standard testing accompanied by inverse numerical modeling of these tests, which is used to obtain relevant material properties. A numerical model composed of a detailed pyrolysis submodel and empirical flame heat feedback submodels, which were developed in this study, is subsequently employed to simulate the early stages of the Room Corner Test, which was selected to represent full‐scale material performance. The results of these simulations demonstrate that this procedure can successfully differentiate between fire growth propensities of several commercially available medium density fiberboards.     

Dextrose monohydrate as a non-animal sourced alternative diluent in high shear wet granulation tablet formulations

The feasibility of dextrose monohydrate as a non-animal sourced diluent in high shear wet granulation (HSWG) tablet formulations was determined. Impacts of granulation solution amount and addition time, wet massing time, impeller speed, powder and solution binder, and dry milling speed and screen opening size on granule size, friability and density, and tablet solid fraction (SF) and tensile strength (TS) were evaluated. The stability of theophylline tablets TS, disintegration time (DT) and in vitro dissolution were also studied. Following post-granulation drying at 60?°C, dextrose monohydrate lost 9% water and converted into the anhydrate form. Higher granulation solution amounts and faster addition, faster impeller speeds, and solution binder produced larger, denser and stronger (less friable) granules. All granules were compressed into tablets with acceptable TS. Contrary to what is normally observed, denser and larger granules (at ≥21% water level) produced tablets with a higher TS. The TS of the weakest tablets increased the most after storage at both 25?°C/60% RH and 40?°C/75% RH. Tablet DT was higher for stronger granules and after storage. Tablet dissolution profiles for 21% or less water were comparable and did not change on stability. However, the dissolution profile for tablets prepared with 24% water was slower initially and continued to decrease on stability. The results indicate a granulation water amount of not more than 21% is required to achieve acceptable tablet properties. This study clearly demonstrated the utility of dextrose monohydrate as a non-animal sourced diluent in a HSWG tablet formulation.