Carbonization and liquid-crystal (mesophase) development. 8. The co-carbonization of coals with acenaphthylene and decacyclene

Several coals of different rank have been carbonized singly and also co-carbonized with acenaphthylene and decacyclene. The resultant cokes were mounted in resin and polished surfaces were examined for optical texture using a polarized-light optical microscope fitted with a half-wave retarder plate. The optical texture can be assessed qualitatively (visually) or quantitatively by a point-counting technique in terms of size and shape of constituent isochromatic anisotropic units. Some cokes from coals were Isotropic. Acenaphthylene was only able to exert a smaller influence than decacyclene on the optical texture of the resultant cokes from co-carbonizations. Decacyclene was able to modify the optical texture for both the low-rank non-fusible and the caking coals. The effects of changing the proportions of coal to additive were examined. Results are interpreted in terms of ‘depolymerization’ of the coal by the action of the additive (as solvent) and also by the action of the additive in modifying the processes of formation of semi-coke via nematic liquid crystals.     

The Structural Elucidation of Oligomeric Blue Dyes Derived from 9-Alkylcarbazoles

Carbazoles react with a variety of one-carbon fragments at the 3- or 3,6-positions to give di- and trimeric products with CH₂: links. These precursors react by losing hydride ion to give blue oligomeric dyes. Carbazoles substituted in the 9-position by CH₂SPh, CH₂SOPh, and CH₂SO₂Ph rearrange to give carbazole oligomers linked at the 3,6-positions. Products are characterised spectrally, and their mechanism of formation is discussed.     

Evaluation of the aromatic structure of coal tar pitch by solid and solution state n.m.r.

Rapid magic angle spinning has been used to obtain sideband-free high field ¹³C n.m.r. spectra of coal tar pitches in the solid state. However, the unfavourable cross-polarization and ¹H relaxation characteristics make it difficult to accurately estimate concentrations of quaternary aromatic carbon using the dipolar dephasing method. The concentrations of bridgehead aromatic carbon in the whole pitch and toluene-insoluble fraction investigated were deduced using a combination of solid and solution state n.m.r. and elemental analyses.     

Why Hydroxamates May Not Be the Best Histone Deacetylase Inhibitors—What Some May Have Forgotten or Would Rather Forget?

Hydroxamate‐based histone deacetylase inhibitors (HDACIs) have been approved as therapeutic agents by the US Food and Drug Administration for use in oncology applications. While the potential utility of such HDACIs in other areas of medicinal chemistry is tremendous, there are significant concerns that “pan‐HDAC inhibitors” may be too broadly acting and/or toxic for clinical use beyond oncology. In addition to the isozyme selectivity challenge, the potential mutagenicity of hydroxamate‐containing HDAC inhibitors represents a major hindrance in their application to other therapeutic areas. Herein we report on the mutagenicity of known hydroxamates, discuss the mechanisms responsible for their genotoxicity, and review some of the current alternatives to hydroxamates. We conclude that the hydroxamate group, while providing high‐potency HDACIs, is not necessarily the best zinc‐binding group for HDACI drug discovery.     

Size-dependent deposition of inhaled nanoparticles in the rat respiratory tract using a new nose-only exposure system

Concerns about the potential health effects of exposure to nanomaterials have led to a growing number of in vivo inhalation toxicity studies using nanoparticle aerosols. Estimates of aerosol deposition within the respiratory tract are important for these studies to enable: (a) the interpretation of the results, in particular, the evaluation of dose–response relationships; (b) comparison with the results of other related studies; and (c) the extrapolation of results from animal models to human. Unfortunately, only a limited number of studies have been undertaken to investigate respiratory tract deposition efficiencies for nano-sized aerosol particles. This is of particular importance as deposition efficiencies are predicted to vary significantly over the nano-size range for some elements of the respiratory tract. In this study, female Wistar-Kyoto rats were exposed in a new design nose-only inhalation exposure system to spark generated radioactive iridium-192 nanoparticle aerosols of four particle sizes chosen to cover the majority of the nano-size range (nominal sizes: 10, 15, 35, and 75 nm). The content of iridium-192 in the lung, head, gastrointestinal tract, and various other organs and tissues was measured. Aerosol deposition efficiencies in the whole respiratory tract and components (head airways, lung, alveolar region, and tracheobronchial region) were estimated and compared with the predictions of the Multiple Path Particle Dosimetry (MPPD) model (v2.11). The experimentally derived deposition efficiencies were broadly consistent with, but typically higher than, model predictions and the results of comparable studies in the literature.

Copyright © 2016 American Association for Aerosol Research     

Electrically conductive adhesives: Effect of particle composition and size distribution

The effects of particle composition and size distribution on the electrical properties of conductive adhesives were studied. Silver-plated glass and silver-plated nickel particles with both narrow (37-44 μm) and broad (< 44 μm) size distributions were dispersed in an epoxy matrix. In all cases, formulations incorporating narrow particle size distributions required greater concentrations of particles to exceed the percolation threshold for electrical conduction than when broad particle distributions were used. Differences between glass and nickel particles were observed and attributed to the higher density of nickel particles, as well as subtle variations in particle size distributions.     

Analysis of wide-angle X-ray diffraction patterns of aligned glassy polymers with particular references to polystyrene

Improvement of WAXD patterns from aligned glassy polymers by a numerical desmearing technique is reported. This gives a fibre type diffraction pattern that can be more easily interpreted than radial or cylindrical distribution functions. Application to atactic and quenched isotactic polystyrene shows that the molecular conformations that are found are in agreement with those deduced from i.r. and n.m.r. spectroscopy. For isotactic polystyrene there is significant agreement between the fibre pattern of the aligned glassy polymer and that of the drawn crystalline polymer.     

Coalification paths of exinite,vitrinite and inertite

Coalification is a burial metamorphic process fundamental to understanding the origin and nature of coals and petroleum. Accurate assessment of Coalification requires removal of the variation in coal properties owing to differences in coal type. This is best achieved by assessing the coal rank of the maceral groups exinite, vitrinite and inertinite (and ultimately the macerals within each group) in terms of maximum reflectance. The mean maximum reflectances of exinite (R?_E max), vitrinite (R?_v max) and inertinite (R?_I max) are highly correlated over the rank range, soft brown coals to low-volatile bituminous coals. A single exinite Coalification break is identified at 0.4 to 0.5% R?_V max. Thereafter, exinite coalification occurs at an increasing rate (R?_E max relative to R?_V max) over the rank range 0.5–2.0% R?_V max, crossing the vitrinite Coalification path at 1.55% R?_V max. A phase of rapid inertinite Coalification (0.7–2.0% R?_I max) occurs between 0.2 and 0.9% R?_V max. Since exinite is a major land-plant source of hydrocarbons, and R?_E max is a sensitive indicator of organic maturation over the range 0.2–1.1% R?_E max, which corresponds to the main phase of oil generation, R?_E max can be a most useful indicator of petroleum generation. The inertinite lnkohlungsprung represents a dramatic compositional change which should be taken into account when considering the origin of inertinite, its utilization properties and the general processes of rank change and organic maturation.     

Polyurethanes derived from caprolactone polyesters and diamines

Thermoplastic, light-stable polyurethanes have been prepared by the interfacial poly-condensation of secondary diamines with the bischloroformates of polyester diols derived from ε-caprolactones. A straight-line relationship was obtained from a logarithmic plot of inherent viscosity versus M _n. The effect of some structural variations on the properties of the polyurethanes is discussed. These variations included the molecular weight of the polyester diol, the initiator used in preparing the polyester diol, the introduction of a methyl substitutent on the caprolactone ring, and the structure of the diamine. Polyurethanes prepared from polyester diols of M _n from 2000–4000 are opaque, stiff materials which undergo a melting transition at 40–50°C. characteristic of the polyester component. Polyurethanes which are flexible and translucent at room temperature are obtained either by using a low molecular weight polyester diol or a copolyester diol containing > 25% methyl ε-caprolactone. The polyurethanes described are soluble in several common solvents and can be cold-drawn to produce material of high tensile strength. Thermal studies using DTA and TGA Show an exothermic reaction starting above 300°C. Rapid weight loss beginning at 300–330°C. and leveling off near 500°C. accounted for 85–90% of the total sample and is attributed to decomposition of the polyester Chains.     

Ignition of droplets of liquid fuels solvent extracted from coal

A single suspended-droplet technique has been used to study droplet combustion of a range of solvent-refined coal extracts in a furnace at 850 °C. The small particles of extract are solid at room temperature but they rapidly liquefy on exposure to the hot furnace environment, permitting the size and mass-time combustion histories to be measured. Their combustion behaviour is discussed in terms of their high aromaticity and comparison with the single droplet combustion of fuel oils of different asphaltene content was used to highlight potential solids emissions problems which may arise when firing in large systems.