Local Structure of Alkaline-Earth Boroaluminate Crystals and Glasses: II, 11B and 27Al MAS NMR Spectroscopy of Alkaline-Earth Boroaluminate Glasses

¹¹B and ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectra of alkaline-earth boroaluminate glasses show that the structure of these glasses are far more complicated than previously thought. The relative concentrations of 3- and 4-coordinated boron vary as found by previous investigators using continuous-wave NMR methods, but the ²⁷Al NMR spectra indicate the presence of Al in 4-, 5-, and 6-fold coordination, in contrast to previous assignments. Analysis of the data based on local charge balance considerations provides a qualitative model that correctly predicts compositional variations of the NMR peak intensities and ²⁷Al chemical shifts for a wide range of boroaluminate glass compositions.     

Mechanical properties of discontinuous fiber reinforced thermoplastics. II. Random-in-plane fiber orientation

The mechanical properties are presented for a series of discontinuous fiber-reinforced thermoplastic composites made with random-in-plane fiber orientation. The matrix and fiber materials were chosen to provide a wide range of strength, modulus, ductility and adhesive properties. In many cases strong, rigid, yet tough composites were fabricated. Strength levels of over 20,000 psi and modulus values over 1,000,000 psi were reached in several systems reinforced with short Kevlar-49 and graphite fibers. A strong dependence of composite strength and modulus on fiber strength and modulus was noted indicating good transfer of load from matrix to reinforcement. Fiber efficiency factors for modulus and strength were calculated for the experimental composite systems and averaged 0.19 and 0.11 respectively. Data were analyzed using basic composite theory. Properties of the experimental composites could not be predicted from constituent properties.     

Ferrocene-functionalized carbon nanoparticles

Carbon nanoparticles were synthesized from natural gas soot and functionalized with ferrocenyl moieties by using 4-ferrocenylphenyldiazonium as the reactive precursor. The incorporation of the ferrocenyl units onto the carbon nanoparticle surface was confirmed by varied spectroscopic measurements. For instance, in FTIR measurements the characteristic vibrational bands of the ferrocenyl and phenyl moieties could be clearly identified. XPS measurements showed that there were approximately 31.9 ferrocenyl units per nanoparticle. UV-vis spectroscopic measurements displayed an absorption band at ca. 465 nm which was consistent with the optical characteristics of ferrocenyl derivatives. Furthermore, with surface functionalization by the ferrocenyl moieties, the photoluminescence of the carbon nanoparticles was found to diminish in intensity and red-shift in energy with the addition of NOBF(4). This was accounted for by the formation of varied electron-accepting moieties on the particle surface, such as positively charged ferrocenium, quinone-like derivatives, and nitrosation of the aromatic rings of the graphitic cores. Interestingly, in electrochemical studies the nanoparticle-bound ferrocenyl moieties were found to exhibit two pairs of voltammetric waves with a difference of their formal potentials at about 78 mV, suggesting nanoparticle-mediated intraparticle charge delocalization at mixed valence as a result of the strong core-ligand covalent bonds and the conductive sp(2) carbon matrix of the graphitic cores. Consistent behaviors were observed in near-infrared measurements, indicating that the particles behaved analogously to a Class I/II mixed-valence compound.     

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.     

Altering the association properties of insulin by amino acid replacement

The importance of Pro^B28 and Lys^B29 on the self-associationof insulin was established by systematically truncating theC terminus of the B chain. The relationship between structureand association was further explored by making numerous aminoacid replacements at B²⁸ and B²⁹ Association was studied bycircular dichroism, size-exclusion chromatography and ultracentrifugation.Our results show that the location of a prolyl residue at B²⁸is critical for high-affinity self-association. Removal of Pro^B28in a series of C-terminal truncated insulins, or amino acidreplacement of Pro²⁸, greatly reduced association. The largestdisruption to association was achieved by replacing Lys^B29 withPro and varying the amino acid at B²⁸ Several of the analogswere predominantly monomers in solutions up to 3 mg/ml. Theseamino acid substitutions decreased association by primarilydisrupting the formation of dimers. Such amino acid substitutionsalso substantially reduced the Zn-induced insulin hexamer formation.The formation of monomeric insulins through amino acid replacementswas accompanied by conformational changes that may be the causefor decreased association. It is demonstrated that self-associationof insulin can be drastically altered by substitution of oneor two key amino acids.     

Impact of dietary n−3 FA deficiency on rat bone tissue FA composition

The effect of dietary n−3 FA deficiency on bone tissue FA composition was evaluated in growing rats. Two mixtures combining hydrogenated coconut oil with safflower oil served as the n−3-deficient dietary treatments and provided two levels of linoleic acid (LA). The n−3 treatments were formulated with added α-linolenic acid (LNA) from flaxseed oil (diet LNA) or LNA plus DHA, and both were balanced for LA. This study showed that bone is sensitive to changes in dietary n−3 FA and that DHA is more effective than LNA in maintaining DHA levels in these tissues.     

Comparison of Sampling Methods for Carbonaceous Aerosols in Ambient Air

Measurement methods for fine particle carbon were compared under field sampling conditions. Sampling methods included filtration, impaction, and adsorption-corrected filtration. Systems were operated side-by-side for nine consecutive days in the Los Angeles Basin. Analytical methods were compared separately. For organic carbon and total carbon, ambient measurements showed greater variability than could be accounted for by differences in analytical methods, and these differences are attributed to sampling methodology. The highest reported concentrations were obtained by quartz filter sampling; the lowest were from the sum of the impactor stages (excluding the quartz afterfilters). Positive artifact from the adsorption of gaseous vapors on quartz fiber filters was significant. However, correction for vapor adsorption by subtraction of the carbon value on the second of two filters in series did not completely eliminate the dependence of the apparent total aerosol carbon concentration on filter face velocity or sample duration