Structural study of hexane-soluble products from hydroliquefaction of three Yallourn brown coal lithotypes over molten salt catalysts

The hexane-soluble fractions of hydroliquefied products from three Yallourn brown coal lithotypes have been separated into five fractions by combined silica-alumina packed column chromatography. Analyses of various fractions by g.c.-m.s. permitted the identification of ≈50 components in the saturate fraction and 40 components in the diaromatic fraction, together with 30 components in the monoaromatics. The components identified were quite similar among hexane-soluble portions of all three lithotypes. A marked predominance of even carbon number alkane (C₂₃-C₂₉) was observed in the hydrocarbon fractions from pale lithotype over $\text{ZnCl}{}_2\text{KCl}$, and medium light lithotype over both pure ZnCl₂ and $\text{ZnCl}{}_2\text{KCl}$. However, medium dark lithotype over both melt catalysts produced a saturate fraction with an odd carbon number(C₂₂-C₂₈) preference. Based on spectral methods, Soxhlet extracts obtained from untreated lithotypes (hexane and benzene solubles) were characterized as complex mixtures of higher molecular weight(300–1000) aliphatic hydrocarbons, which were supposed to be a precursor of the saturates produced from the corresponding lithotype in the catalytic hydroliquefaction.     

Antitumor activity of synthetic alkylphospholipids with or without PAF activity

1-O-Octadecyl-2-O-methyl-sn-glycero-3-phosphocholine (ET-18-OMe) has been reported to possess definite antitumor activity in vivo. Twenty-two alkyl lysophospholipid analogs were chemically synthesized, and their antitumor activity against mouse experimental tumors (Sarcoma 180, MM46, P388) was examined. Among them, 1-O-octadecyl-2-O-acetoacetyl-rac-glycerol-3-phosphocholine was found to show antitumor activity similar to ET-18-OMe with less acute toxicity. Intravenous injection of the ET-18-OMe withsn-3 configuration retarded the subcutaneous growth of Sarcoma 180 cells effectively, while the growth inhibition by thesn-1 isomer was much less effective. This stereospecificity was similar to that observed in their activities as platelet-activating factor (PAF) agonists. The acetoacetyl compound, another PAF agonist, showed similar stereospecific antitumor action in vivo. These findings suggest that some alkyl lysophospholipids may activate host cells to a cytostatic stage against tumor cells in vivo through binding to a PAF receptor. Our preliminary results indicated that the responsible cells under these conditions might be primarily immature macrophages present in the bone marrow. No appreciable or even adverse stereospecificity was observed in the different sets of experiments where the activity of ET-18-OMe against MM46 tumor cells in vivo or the direct cytotoxicity against human promyelocytic leukemia HL-60 cells in vitro was examined. Under, some conditions, the antitumor activity of ET-18-OMe in vivo may be revealed through direct cytotoxicity and/or modulation of the host defense system by “nonspecific” mechanisms. Some alkylphospholipids without PAF activity may also show antitumor activity through similar, “nonspecific” mechanisms.     

E.s.r. study of annealing and melting effects on the molecular motion of spin trapped chain-end radicals located on the polyethylene surface

E.s.r. spectra of chain-end spin labels on the surface of polyethylene powder were obtained for high and low density polyethylene samples at various stages of heat treatment process. The subsequent crystalline structures of the samples were examined with wide angle and small angle X-ray diffraction spectra. The effects of annealing on the motion of the labels were dependent on annealing temperature and the type of the samples. Higher temperature annealing decreased the rotational correlation times (τ_c) and their activation energy in high density polyethylene but did not affect those of low density polyethylene. Melting decreases the values of τ_c and ΔE for both high an low density polyethylene samples. The cause of these decreases were attributed to the changing of the sites of the chain-end labels. The motion of the labels appeared to be influenced by the local segmental motion of the polymer main chains.     

Synthesis of poly(tetrahydrofuran-b-ε-caprolactone) macromonomer via the Sml2-induced transformation

Summary A novel well-defined macromonomer consisting of different types of monomers in polymerization mechanisms was synthesized for the first time through the SmI₂-induced transformation. The macromonomer, -methacryloylpoly-(tetrahydrofuran-b--caprolactone), was prepared by the reaction of methacryloyl chloride with living poly(tetrahydrofuran-b--caprolactone) [poly(THF-b-CL)] which was obtained by the two-electron reduction of the cationic growing center of poly(THF) by samarium iodide (SmI₂) followed by the polymerization of CL. ¹H NMR analysis indicated the quantitative introduction of the methacryloyl group onto the polymer end. The molecular weight distribution of the macromonomer was relatively narrow, and the unit ratio of THF to CL could be controlled by both polymerization time of THF and the amount of CL, resulting from the living nature of both CL- and THF-polymerizations. Radical copolymerization of the produced macromonomers with methyl methacrylate in the presence of AIBN resulted in a polymethacrylate backbone grafted with poly(THF-b-CL) block copolymers.     

Novel stabilization system for polypropylene via the Ziegler–Natta catalyzed polymerization in the presence of aluminum aryloxide

The aluminum aryloxide was prepared via the reaction of phenolic antioxidant, 3‐(3,5‐di‐t‐butyl‐4‐hydroxyphenyl)‐N‐octadecylpropionamide, with triethyl aluminum. Propylene polymerization using supported Ziegler–Natta catalyst systems was carried out in the presence of the antioxidant or its aluminum aryloxide. Although the antioxidant gave rise to decrease in catalyst yield and change in hydrogen response, the aluminum aryloxide had no influence on the catalytic polymerization behavior, and thus the obtained polymer characteristics such as molecular weight, polydispersity, and meso pentad as a stereoregularity were comparable to that polymerized without the antioxidant and the aluminum aryloxide. Polypropylene obtained in the presence of the aluminum aryloxide was well stabilized for oxidation and its stability was over 1000 h at 100°C (estimated to be over 30 years at room temperature). © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1350–1358, 2006     

Mechanical properties of porous titanium compacts prepared by powder sintering

Porous Ti compacts for biomedical applications are successfully fabricated in the porosity range from 5.0 to 37.1 vol% by controlling sintering conditions and Ti powder sizes. Young’s modulus and bending strength at the porosity of around 30 vol% are found to be similar to those of human cortical bone.     

Topology optimization for fluid–thermal interaction problems under constant input power

This paper deals with density-based topology optimization considering fluid and thermal interactions, in which the Navier–Stokes and heat transport equations are coupled. We particularly focus on designing heat exchangers. In the engineering context, heat exchangers are designed while considering a certain amount of input power. Therefore it is important to maximize the performance of a heat exchanger under a constant input power. In this paper we propose a way to control the input power by introducing an extra integral equation. To be more precise, in the fluid analysis, the inlet pressure is determined by solving the extra integral equation together with the Navier–Stokes equation. By doing this we can keep the inlet power constant even when the flow channels are changed in the optimization process. Consequently, the system of equations of the fluid field takes an integrodifferential form. On the other hand, in the heat transport analysis, a single governing equation is defined for simultaneously modeling both the solid and fluid parts. The design variable is a fluid fraction whose distribution represents the topology of the solid and fluid domains. When designing heat exchangers, two different heat conditions are considered in the formulation of the optimization problems, namely temperature-dependent and temperature-independent heat sources. Through the numerical examples for designing flow channels in a heat exchanger, it is shown that distinct topologies can be obtained according to the input power and the heat source conditions.     

Incoherent-only joint-transform correlator

An incoherent-only optical and electronic digital joint-transform correlator is proposed. A technique for the removal of extraneous signals inherent in the incoherent-only joint-transform correlator is also presented. A computer simulation and experimental results confirm the performance of the proposed incoherent-only joint-transform correlator.     

Revolving Vernier Mechanism Controls Size of Linear Homomultimer

A new kind of the Vernier mechanism that is able to control the size of linear assembly of DNA origami nanostructures is proposed. The mechanism is realized by mechanical design of DNA origami, which consists of a hollow cylinder and a rotatable shaft in it connected through the same scaffold. This nanostructure stacks with each other by the shape complementarity at its top and bottom surfaces of the cylinder, while the number of stacking is limited by twisting angle of the shaft. Experiments have shown that the size distribution of multimeric assembly of the origami depends on the twisting angle of the shaft; the average lengths of the multimer are decamer, hexamer, and tetramer for 0°, 10°, and 20° twist, respectively. In summary, it is possible to affect the number of polymerization by adjusting the precise shape and movability of a molecular structure.