Observation of single-walled carbon nanotubes by photoemission microscopy

Single-walled carbon nanotube networks grown on SiO₂ pillars were studied by means of scanning photoemission microscopy. The individual nanotubes or nanotube bundles growing from the pillar tops were observed in C 1s images. Band bending near catalytic Fe/nanotube contacts in an end-bonded configuration was studied by measuring C 1s spectra along the tube axes. Within our experimental resolution, no band bending was observed. This implies that the depletion width is less than the spatial resolution of the scanning photoemission microscope (90 nm) or that the amount of the band bending is less than 0.1 eV.     

Crystalline complex between poly(γ-methyl l-glutamate) and dimethyl phthalate

The crystalline complex between poly(γ-methyl l-glutamate) (PMLG) and dimethyl phthalate (DMP) has been formed in films cast from a solution in dichloroethane. It has the stoichiometry of 1 mol of DMP to three or four residues of PMLG and shows two definite characteristics in X-ray diffraction patterns; one is the large hexagonal unit cell with the edge of around 28 Å and another the ‘extra’ 5.07 Å meridional reflection which can not be interpreted by a PMLG α-helical conformation. The structural examination for the films with various DMP contents is carried out by X-ray, viscoelastic, and d.s.c. measurements and the following structure is proposed for the crystalline complex. Four PMLG are associated to form a group which is hexagonally packed and DMP molecules, located in the gaps between groups, form a specific favourable helical structure along PMLG chains in which the van der Waals stacking of benzene rings of DMP is significant.     

Critical temperature for production of MAG by esterification of different FA with glycerol using <Emphasis Type="Italic">Penicillium camembertii</Emphasis> lipase

Production of MAG by a lipase-catalyzed reaction is known to be effective at low temperature. This phenomenon can be explained by assuming that synthesized MAG are excluded from the reaction system because MAG, which have low m.p., are solidified at low temperatures. Consequently, MAG are efficiently accumulated and do not serve as the precursor of DAG. If this hypothesis is correct, the critical temperature for MAG production, defined as the highest temperature at which DAG synthesis is repressed, should depend on the m.p. of the MAG. Esterification of FFA with glycerol using Candida rugosa, Rhizopus oryzae, and Penicillium camembertii lipases produced MAG efficiently at low temperatures. However, Candida lipase showed very low esterification activity at high temperatures (>20°C), and Rhizopus lipase produced not only MAG but also DAG even at low temperatures. Meanwhile, P. camembertii lipase catalyzed synthesis of MAG only from FFA and glycerol at low temperatures, although the enzyme catalyzed synthesis of DAG from MAG in addition to synthesis of MAG at high temperatures. We thus studied the effect of temperature on esterification of C₁₀−C₁₈ FFA with glycerol using Penicillium lipase as a catalyst and determined the critical temperatures for production of MAG. The critical temperature for production of each MAG showed a linear correlation with m.p. of the MAG, which supported the hypothesis. In addition, because the m.p. of MAG are estimated from that of the constituent FA, the optimal temperature for production of MAG can be predicted from the m.p. of the FFA used as a substrate.     

Stereochemistry and mechanism of the hydrogenation of dialkyl cyclohexenes

In order to investigate the steric effect of the substituents to determine the product distribution, disubstituted cyclohexenes were hydrogenated over several transition metal catalysts. Some cyclohexenes which have two large substituents at the vicinal carbon atoms, at least one of which is trigonal, were not hydrogenated over Raney Ni at all but were hydrogenated over Pt catalyst under our experimental conditions. Presumably, the stereoselectivity depends on the competitive operation of the torsional angle strain and the catalyst hindrance with substituents. In the hydrogenation over Pd catalyst, thermodynamically more stable products were dominant at the standard condition but at high substrate to catalyst ratio the less stable products were slightly preferred. No appreciable stereoselectivity was observed in the hydrogenation of 1,4-disubstituted cyclohexenes.     

Solid-state high-resolution 13C-NMR studies of regenerated cellulose samples with different crystallinities

Summary CP/DD/MASS ¹³C-NMR spectra have been obtained for regenerated cellulose samples with different crystallinities as well as for cotton, -D-glucose, -D-cellobiose, and cellopentaose. The spectra of the regenerated cellulose samples exhibit broad multiplicities of the C-4 and C-6 resonance lines in a similar manner as those of native cellulose samples such as cotton and ramie, and, in addition, another broad tailing of the C-1 resonance. Since these multiplicities change linearly with crystallinity, it is concluded that they are ascribed to the contributions from the crystalline and noncrystalline components. Effects of hydrogen bonds and conformations of the -1,4-glycosidic linkage on the chemical shifts are also discussed.     

Synthesis of γ-Ga2O3–Al2O3 Solid Solutions by the Glycothermal Method

The reaction of mixtures of aluminum isopropoxide and gallium acetylacetonate in 1,4-butanediol or 1,5-pentanediol at high temperatures (glycothermal reaction) directly gave the γ-Ga₂O₃–Al₂O₃ solid solutions, which had high catalytic activities for selective reduction of NO using methane as the reducing agent. However, the reaction with a higher Al/(Ga+Al) charged ratio yielded the glycol derivative of boehmite as a by-product and the catalytic activity of the solid solution decreased. Therefore, synthesis of the solid solution using various glycols was examined and it was found that solid solutions with high Al contents without contamination of the glycol derivative of boehmite were obtained by using 1,6-hexanediol as a reaction medium. The solid solution exhibited a higher NO conversion than that synthesized in other glycols.     

Characteristic properties of cutting fluid additives derived from the adducts of diamines and acid chlorides

A number of N,N′-diacylalkyldiamines were prepared from the reaction of acid chlorides with 1,8-diaminooctane and 1,12-diaminododecane and screened for anti-rust properties and antimicrobial activity in spent coolants of water-based cutting fluids. Aqueous solutions of N,N′-dihexanoyl-1,8-diaminooctane and N,N′-isobutyroyl-1,12-diaminododecane showed good anti-rust properties for water-based cutting fluids. Aqueous emulsions of N,N′-dibutyroyl-, dipentanoyl-, dihexanoyl- and dioctanoyl-1,12-diaminododecane showed good lubricities and antimicrobial activity for water-based cutting fluids.     

Hydrothermal Formation of Hydroxyapatite Layers on the Surface of Type-A Zeolite

Type-A zeolite evenly covered with hydroxyapatite thin layers was prepared using hydrothermal treatment at 120°C for 8 h under autogenous pressure. The hydroxyapatite needlelike nanocrystals, 100–200 nm in diameter and 30 nm in thickness, were grown under the reaction between discharged Ca²⁺ ions from type-A zeolite and PO₄³⁻ ions in (NH₄)₃PO₄ solution. The preferential orientations of the c -axis of hydroxyapatite crystals perpendicular to a zeolite surface were observed using transmission electron microscopy. The crystal structure of type-A zeolite was not destroyed under the reaction, but the surface morphology was changed only with complete covering of scaly hydroxyapatite particles.     

Characterization of n-hexadecylalkylamine-intercalated graphite oxides as sorbents

Adsorption properties of graphite oxides hydrophobized by n-hexadecylamine, (C16)_xGO, were investigated using pyrene molecules as a model of nonionic organic contaminants. A large quantity of pyrene (28.5 mg/g) was adsorbed from a water-ethanol mixture (1:2) containing 2 mM of pyrene when (C16)_0.6GO was used. The isotherm of pyrene adsorption was better described by Freundlich equation rather than Langmuir equation, which indicated a single adsorption mechanism was involved. The change in the amount of adsorbed pyrene as a function of amine content in GO was very similar to that which occurs upon introduction of pyrene into (C16)_xGO films from chloroform solution, as determined by X-ray measurements. This suggests that pyrene molecules were adsorbed not only on the outer surface but also within the interlayer space of the intercalation compound. Swelling of the intercalation compound by ethanol can render the interlayers more organophilic and make access to hexadecylamine molecules bonded to the graphite oxide layer easier for pyrene molecules, especially in (C16)_xGOs with lower amine contents.     

Determination of fatty acid composition by gas chromatography: II. Analysis with use of flame ionization detector

In this study known mixtures of four or five fatty acid methyl esters were analyzed collaboratively by gas chromatography with flame ionization detectors. The experimental data was treated statistically to examine inter- and intralaboratory scattering. More-over the effect of the use of correction factors was investigated. Even if only the specific analytical values that scattered a little were chosen, the averages of such values did not always approach the actual values. In some laboratories a sort of regularity was observed in the deviation of analytical values from real values throughout the analyses of four samples. The application of correction factors to the analytical values obtained by these laboratories resulted in a considerable decrease of interlaboratory scattering and deviation from the real values. When a constant amount of sample was injected, intralaboratory scattering was decreased, whereas interlaboratory scattering was not. Injection of large sample sizes caused deviation. From this collaborative study it was recommended that 0.5–1.0 μl of 20% solution be injected. Presented at the JOCS-AOCS Joint Meeting, Los Angeles, April 1972.