Thickening process of polyethylene single crystals at an early stage of annealing

By the use of a position sensitive proportional counter, changes in small and wide angle X-ray scattering during annealing of polyethylene single crystal mats were measured from the start in successive spans of very short measuring time. At high temperatures, the long period relating to stacking of lamellae rapidly increased at an early stage, passed through a plateau, and thereafter again increased gradually. With a decrease in annealing temperature, the amount of its first rapid increase was reduced and the plateau changed into an ascending slope. At much lower annealing temperatures, the long period increased following the logt law after an induction time. The integral breadth of a peak corresponding to the long period first increased rapidly, simultaneously with the rapid increase in the long period, and thereafter decreased. Wide angle X-ray measurement showed that the integrated intensity of 110 reflection first decreased and then increased during annealing at high temperatures. This fall and rise process was more marked, when the annealing temperature is higher and the initial thickness of lamellae is smaller. From these observations, it was inferred that in the thickening process, stacking order of lamellae at first decreased because of rapid reorganization due to partial melting or melt-recrystallization and subsequently increased through increasing evenness of lamellar thickness.     

Radiation-induced copolymerizations of perfluorovinyl acetic acid and its methyl ester with α-olefin

Homopolymerizations and copolymerizations of perfluorovinyl acetic acid (FVA) and its methyl ester (MFVA) were carried out by γ radiation at a temperature of 25°C, a dose rate of 1 × 10⁶ rad/hr, and FVA/α-olefin and MFVA/α-olefin ratios of 10/90-90/10 in the monomer mixture. FVA and MFVA gave small quantities of brown and greasy low-molecular-weight homopolymers. The polymerization rates of both FVA and MFVA were extremely small, as shown by the maximum G value of monomer consumption of 12. FVA and MFVA reacted with α-olefin to form waxlike copolymers. The copolymerization rates of both FVA and MFVA with α-olefin were remarkably larger than those of the homopolymerizations, particularly with ethylene. The polymer compositions of FVA/ethylene or MFVA/ethylene was nearly 1/2 over a wide range of the monomer compositions. The Mayo–Lewis method gave negative r₁ (FVA) and r₁ (MFVA). The polymer composition curves could be well interpreted by introducing the penultimate model.     

Visualization and laser measurements on the flow field and sand movement on sand dunes with porous fences

The installation of windbreak sand fences around sand dunes is one of the most promising methods to suppress windblown sand movement. In the study reported in this paper, we investigated the influence and validity of a small fence mounted on a model sand dune, in order to understand the fence’s suppression mechanism on the sand movement. The flow field around the dune and the process of sand-dune erosion were measured using LDV, PIV, and laser-sheet visualization techniques. A non-porous fence was found to suppress sand movements in its upstream area, but to enhance erosion downstream of the fence. This intensive erosion was caused by separated shear flow from the leading edge of the fence. In this study, four levels of porosity rate of the fence were tested. The fence-porosity dependences of the turbulent flow field and the erosion were discussed. The shapes of eroded sand dunes were found to depend on the porosity rate. The relationship between the sand-dune erosion and the flow field around the dune was illustrated with schematic diagrams. We concluded that the most desirable fence porosity should be 30% in order to avoid dune erosion if installed at a middle height on the stoss surface of a dune. This porosity provides a mean velocity reduction with avoiding a separated flow, although the flow bleeding through the porous fence is accompanied by grid turbulence and induces serious erosion in a narrow space behind the fence. Furthermore, we confirmed that the empirical correlation of the critical friction velocity can be applied to sand movements influenced by a fence.     

High resolution electron microscopy of (SN)x

Pristine and iodinated (SN)_x were studied by high resolution electron microscopy. High resolution electron micrographs showing lattice fringes up to 0.22 nm were obtained. In these electron micrographs, the texture of (SN)_x crystals was elucidated to be fibrillar or mosaic; the lattice fringes were observed in domains extended along the molecular axis (b-axis) and very narrow in the perpendicular direction. Each crystallite varied from place to place in size but maintained the b-axis orientation.The high resolution image of iodinated (SN)_x did not show directly the location of iodine atoms and their presence was deduced only from the optical transform of the image. The optical transform showed that iodine atoms were not intercalated uniformly, but localized at the skin region on (SN)_x fibers, where the crystal lattice was highly distorted. Then the iodination of (SN)_x is supposed to result in the destruction of the crystal lattice by invasion of iodine atoms or to take place preferentially at a distorted crystal region.     

A novel synthesis of benzo- and indolo[a]quinolizidines by intramolecular diels-alder reaction of l-azadienes

Intramolecular Diels-Alder reaction of l-azadienes was conducted by heating the α,β-unsaturated amides (2a ～ d and 6) in the presence of trimethyl- chlorosilane, triethylamine and zinc chloride to give benzo- and indolo[a]- quinolizidines (5a ～ e and 7).     

Determination of benzophenones in river-water samples using drop-based liquid phase microextraction coupled with gas chromatography/mass spectrometry.

In this study, a fast, simple and highly sensitive method that employs liquid phase microextraction (LPME)-GC/MS was developed to analyze trace benzophenones (BPs) in river-water samples. The tip of a 10-microl microsyringe filled with toluene (3 microl) was inserted into 2 ml of a river-water sample, and fixed at 5 mm below the water surface of the sample. A toluene droplet was made on the tip of the syringe, and extraction was conducted while agitating at 500 rpm for 15 min. After extraction, 2.0 microl of the extract was put into the syringe again, and directly introduced to GC/MS. The limits of detection (S/N = 3) and quantification (S/N >10) of BPs were 10 and 50 pg ml(-1), respectively. The results of a recovery test ranged over 93.3 - 101.1% (RSD, less than 10%; n = 6). The results of BPs determinations in the river-water samples showed that BPs (ND - 68.9 pg ml(-1)) were detected.     

Syntheses of cerulenin and its analogs. II. Synthesis and biological activity of dl-carbacerulenin, a carbocyclic analog of cerulenin.

2,3-Epoxy-4-hydroxy-4-((E,E)-3,6-octadienyl)cyclopentanone (dl-carbacerulenin 5) was synthesized via the epoxyketones 15a and 15b as a mimic of the active form of the antibiotics cerulenin 1, a potent inhibitor of fatty acid synthetase (FAS). The monobenzyl ethers (12 and 13), synthetic intermediates of 15, were prepared by direct benzylation of the epoxycyclopentene (7). Inhibitory activity of synthesized 5 toward yeast FAS was less than that of cerulenin by a factor of 1000.     

Immobilization of 1-nitroso-2-naphthol on surfactant-coated alumina for the collection of traces of cobalt(II) ions

Positively charged alumina surfaces were coated with sodium dodecyl sulfate, into which 1-nitroso-2-naphthol was immobilized. The alumina particles were effectively used for the collection of nanogram amounts of cobalt(II) from aqueous solutions of pH 1–2.5. The method has been applied to the electrothermal AAS determination of cobalt in high-purity zinc metal.