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.     

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.     

Synthesis of random or tapered solution styrene–butadiene copolymers in the presence of sodium dodecylbenzene sulfonate as a polar modifier

Random or tapered solution styrene–butadiene copolymer (SSBR) is very difficult to prepare in an isothermal batch process without the use of polar modifiers because of the diverse reactivity ratios of the styrene and the butadiene in hydrocarbon solvents. In the presence of polar modifiers, the random SSBR can be synthesized by anionic living polymerization with the variety of microstructures, which results in the change of glass transition temperature (T_g). This article will discuss the use of sodium dodecylbenzene sulfonate as a polar modifier in isothermal batch process that controls the microstructure of the SSBR resulting in a random as well as tapered SSBR with low T_g (?67°C to ?80°C). The T_g of SSBR was controlled by the styrene content rather than the microstructure of polybutadiene. Physical properties of SSBR compounding were discussed for tire tread applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Development of a coordination chemistry-based approach for functional supramolecular structures

The weak-link approach (WLA) to supramolecular assemblies allows for the design of multimetallic two- and three-dimensional arrays, host-guest architectures, sensors, catalysts, switches, and signal amplification devices. This Account describes the course of our investigations in this area beginning with the development of a chemical tool kit of building blocks consisting of multiple metals and ligands. These building blocks can be rationally mixed and matched to provide structures with a wide range of properties that have been used to develop functional supramolecular architectures, including chemical sensors and allosteric catalysts.     

Electron transfer/transport at metal-molecule interfaces probed by femtosecond time-resolved two-photon photoemission: Heptane and fullerene on Au(111)

Electron transfer and transport at metal-molecule interfaces has been a central problem in a number of disciplines. There is renewed interest in this problem from the rapidly growing field of molecule-based electronics, where the so-called “contact problem” is usually probed in transport measurements. Here, we probe interfacial electron transfer/transport using time-resolved two-photon photo-emission spectroscopy. Such an approach allows us to quantitatively measure the energetic alignment of occupied and unoccupied molecular orbitals to the metal Fermi level, the electronic coupling strength (or spectral density) between the molecular orbital and the metal substrate, and electronic-nuclear coupling leading to dynamic localization. These three types of information are in fact key ingredients in quantitative theories for electron transfer and transport at molecule-metal surfaces. Recent examples from our laboratory are used to illustrate the point. They include femtosecond dynamics of image potential resonances on heptane-covered Au(111) and exciton relaxation dynamics in C₆₀ epitaxial films on Au(111). On heptane/Au(111), the lifetime of the n = 1 image potential resonance increases from 52 fs at one monolayer (ML) coverage to 700 fs at 2 ML and 2.8 ps at 3 ML. On C₆₀/Au(111), the Frenkel exciton (involving the LUMO+1 level) couples over long distance to the metal substrate, with lifetime of 350 fs at 30 ML to 80 fs at 2 ML coverage. The film-thickness-dependent decay dynamics in both cases can be attributed to interfacial electron transfer. Fitting the distance-dependent electron transfer rates to a simple exponential function gives the characteristic distance parameter of ß = 0.6 ± 0.1 and 0.023 ± 0.005 Å⁻¹ for heptane- and C₆₀-covered Au(111), respectively. The difference in the ß parameters illustrates the essential role of the electronic structure of molecules in mediating interfacial electron transfer/transport.     

Wax Ester Rich Oil From The Marine Crustacean,Calanus finmarchicus,is a Bioavailable Source of EPA and DHA for Human Consumption

Oil from the marine copepod, Calanus finmarchicus, which contains >86 % of fatty acids present as wax esters, is a novel source of n‐3 fatty acids for human consumption. In a randomized, two‐period crossover study, 18 healthy adults consumed 8 capsules providing 4 g of Calanus^® Oil supplying a total of 260 mg EPA and 156 mg DHA primarily as wax esters, or 1 capsule of Lovaza^® providing 465 mg EPA and 375 mg DHA as ethyl esters, each with an EPA‐ and DHA‐free breakfast. Plasma EPA and DHA were measured over a 72 h period (t = 1, 2, 4, 6, 8, 10, 12, 24, 48, and 72 h). The positive incremental area under the curve over the 72 h test period (iAUC_{0‐72 h}) for both EPA and DHA was significantly different from zero (p < 0.0001) in both test conditions, with similar findings for the iAUC_{0–24 h} and iAUC_{0–48 h}, indicating the fatty acids were absorbed. There was no difference in the plasma iAUC_{0–72 h} for EPA + DHA, or DHA individually, in response to Calanus Oil vs the ethyl ester condition; however, the iAUC_{0–48 h} and iAUC_{0–72 h} for plasma EPA in response to Calanus Oil were both significantly increased relative to the ethyl ester condition (iAUC_{0–48 h}: 381 ± 31 vs 259 ± 39 μg*h/mL, p = 0.026; iAUC_{0‐72 h}: 514 ± 47 vs 313 ± 49 μg*h/mL, p = 0.009). These data demonstrate a novel wax ester rich marine oil is a suitable alternative source of EPA and DHA for human consumption.     

Effects of diet type and supplementation of glucosamine, chondroitin, and MSM on body composition, functional status, and markers of health in women with knee osteoarthritis initiating a resistance-based exercise and weight loss program

Background

The purpose of this study was to determine whether sedentary obese women with knee OA initiating an exercise and weight loss program may experience more beneficial changes in body composition, functional capacity, and/or markers of health following a higher protein diet compared to a higher carbohydrate diet with or without GCM supplementation.

Methods

Thirty sedentary women (54 ± 9 yrs, 163 ± 6 cm, 88.6 ± 13 kg, 46.1 ± 3% fat, 33.3 ± 5 kg/m²) with clinically diagnosed knee OA participated in a 14-week exercise and weight loss program. Participants followed an isoenergenic low fat higher carbohydrate (HC) or higher protein (HP) diet while participating in a supervised 30-minute circuit resistance-training program three times per week for 14-weeks. In a randomized and double blind manner, participants ingested supplements containing 1,500 mg/d of glucosamine (as d-glucosamine HCL), 1,200 mg/d of chondroitin sulfate (from chondroitin sulfate sodium), and 900 mg/d of methylsulfonylmethane or a placebo. At 0, 10, and 14-weeks, participants completed a battery of assessments. Data were analyzed by MANOVA with repeated measures.

Results

Participants in both groups experienced significant reductions in body mass (-2.4 ± 3%), fat mass (-6.0 ± 6%), and body fat (-3.5 ± 4%) with no significant changes in fat free mass or resting energy expenditure. Perception of knee pain (-49 ± 39%) and knee stiffness (-42 ± 37%) was decreased while maximal strength (12%), muscular endurance (20%), balance indices (7% to 20%), lipid levels (-8% to -12%), homeostasis model assessment for estimating insulin resistance (-17%), leptin (-30%), and measures of physical functioning (59%), vitality (120%), and social function (66%) were improved in both groups with no differences among groups. Functional aerobic capacity was increased to a greater degree for those in the HP and GCM groups while there were some trends suggesting that supplementation affected perceptions of knee pain (p < 0.08).

Conclusions

Circuit style resistance-training and weight loss improved functional capacity in women with knee OA. The type of diet and dietary supplementation of GCM provided marginal additive benefits.

Trial Registration

ClinicalTrials.gov: NCT01271218     

Buckling initiation and displacement dependence in compression of vertically aligned carbon nanotube arrays

Carbon nanotube (CNT) arrays have shown the remarkable ability to react as foam-like structures and exhibit localized buckling coordinated within specific regions. Here, we report on the low-cycle compression of bulk vertically aligned CNT arrays to observe initiation and growth of the buckling as a function of compressive strain. A critical strain is found above which the buckling region length increased and below which it remained at or below the applied strain. As previously observed, the buckling region of the CNT array propagates from the surface where growth occurred, which, in the test specimen, is a free surface and later receives compressive contact by a polished silicon substrate. The results are corroborated with nanoindentation on the surfaces, which indicate a stiffening of the near surface with increasing applied strain. Observation and results of the buckling region nature are important for applications of nanotube arrays as energy absorbing cushions, tunable dampers, thermal contacts, or in sliding contact.     

Size-dependent antimicrobial properties of sugar-encapsulated gold nanoparticles synthesized by a green method

The antimicrobial properties of dextrose-encapsulated gold nanoparticles (dGNPs) with average diameters of 25, 60, and 120 nm (± 5) and synthesized by green chemistry principles were investigated against both Gram-negative and Gram-positive bacteria. Studies were performed involving the effect of dGNPs on the growth, morphology, and ultrastructural properties of bacteria. dGNPs were found to have significant dose-dependent antibacterial activity which was also proportional to their size. Experiments revealed the dGNPs to be bacteriostatic as well as bactericidal. The dGNPs exhibited their bactericidal action by disrupting the bacterial cell membrane which leads to the leakage of cytoplasmic content. The overall outcome of this study suggests that green-synthesized dGNPs hold promise as a potent antibacterial agent against a wide range of disease-causing bacteria by preventing and controlling possible infections or diseases.