N.m.r. study of US Eastern and Western shale oils produced by pyrolysis and hydropyrolysis

Shale oils produced from US Eastern and Western oil shales by pyrolysis and hydropyrolysis processes have been investigated by both ¹H and ¹³C high-resolution n.m.r. techniques. Eastern shale oils produced by hydropyrolysis, and subsequently hydrotreated, were also included. From the n.m.r. data of the shale oils, the average molecular structure parameters were calculated. These parameters quantitatively represent the differences observed in the n.m.r. spectra of the various shale oils because of changes in the chemical composition. Mol percentages of aromatics, olefins, and alkanes were also determined for the shale oils, and show that the composition of the shale oil is dependent upon the geographic origin of the oil shale, the pyrolysis method, and the hydrogenation process. In addition to the study of shale oils, solid-state ¹³C n.m.r. spectra of Eastern and Western oil shales before and after pyrolysis and hydropyrolysis were obtained. The spectral data show that the carbon aromaticities for the Eastern oil shales and shale oils are higher than for the Western oil shale and shale oils. The data also show that hydropyrolysis relative to pyrolysis reduces the amount of residual organic carbon remaining on the spent shales. Carbon aromaticity data for both oil shale and shale oil suggest that the organic moieties present in kerogen may be retained in the shale oils to a greater extent after hydropyrolysis than after pyrolysis.     

SIMULATION OF LIGNIN PYROLYSIS

Model compound pyrolysis reaction pathways and kinetics were used in simulation of both native (e.g.. milled wood) and Kraft lignin thermolyses where either only primary or also secondary reactions are important.

Predicted products fell into one of permanent gases, tight liquids, phenolics and carbonaceous residue fractions. Product yields were more dependent on lignin type than on reaction environment.

Comparison of simulation predictions with experimental pyrolyses of actual lignins, accomplished in terms of both product identities and yields, is encouraging. It is noteworthy that the simulations are strictly a priori and incorporate no actual lignin pyrolysis information.     

Oviposition preference of the diamondback moth (Plutella xylostelld) unaffected by the presence of conspecific eggs orBacillus thuringiensis

Neither toxins fromBacillus thuringiensis Berliner nor conspecific eggs deterred oviposition by the diamondback moth,Plutella xylostella (L.) (Lepidoptera: Plutellidae), in laboratory choice tests. The finding that toxins did not deter oviposition by moths from a susceptible line shows that oviposition preference and larval survival were not associated in this line. Selection for larval resistance to toxins did not significantly alter oviposition preference, which rules out a strong genetic correlation between larval performance and oviposition preference. Failure of conspecific eggs to deter oviposition may not represent lack of association of preference and performance because other evidence suggests that larval performance may not be greatly affected by larval density. These results suggest that the ability of refuges to slow evolution of physiological resistance toB. thuringiensis toxins will not be magnified by an oviposition preference for untreated foliage.     

Metal Electrodes Integration on Macroporous Silicon: Pores Distribution and Morphology

ABSTRACT: In this work a new approach for the one step integration of interdigitated electrodes on macroporous silicon substrates is presented. Titanium/gold interdigitated electrodes are used to pattern p-type silicon substrates prior the anodization in a organic electrolyte. The electrolyte characteristics, conductivity and pH, has been found to affect the adherence of the metal layer on the silicon surface during the electrochemical etching. The impact of the metal pattern on size distribution and morphology of the resulting macroporous silicon layer is analyzed. A formation mechanism supported by finite element simulation is proposed.     

Drying and collapse of hollow latex

Hollow latex particles are used as white pigments for paints and paper coatings. In the coating dispersion, each hollow particle is filled with water. As the coating dries, water vacates the latex, leaving an air-filled void sized to scatter light (~0.5 μm) within each particle. Examinations of dried coatings reveal that hollow particles can collapse, decreasing their light scattering efficiency. Cryogenic scanning electron microscopy (cryoSEM) was used to characterize the microstructure of coatings containing hollow latex during drying. Images suggest latex voids empty after air invades into the coating interstitial space and collapse occurs late in the drying process. The effects of temperature (10–60°C), humidity (20–80%), and binder concentration (0–30 wt%) on particle collapse were also studied through SEM of dried coating surfaces. High drying temperature, high humidity, and low binder concentrations promoted collapse. For hollow latex particles with porous shell walls, temperature and humidity had little effect, whereas binder increased collapse. From these results, a theoretical model is proposed. During drying, diffusion of water from the particle creates a vacuum inside the latex. The vacuum is either relieved by nucleation of a gas bubble from the dissolved air in the water-filled particle or it causes the particle to collapse by buckling.     

Experimental validation studies on a multi-dimensional and multi-scale population balance model of batch granulation

In this study, a dynamic model is presented for the granulation process, employing a three-dimensional population balance framework. As a first attempt to account for the multi-scale character of the process, the nucleation and aggregation kernels used in the population balance model are derived using mechanistic representations of the underlying particle physics such as wetting kinetics and energy dissipation effects. Thus, the fundamental properties of the powder and the liquid were used as parameters in the model to predict the granulator dynamics and granule properties. The population balance model is validated against experimental data from a calcite/PVOH-H₂O recipe obtained using a lab-scale drum granulator for granule size, fractional binder content and porosity. A reasonably good agreement between experimental and simulation results were obtained for the granule size distribution under different experimental conditions. In addition, accurate model predictions were made for the evolution of the average properties (i.e., size, fractional binder content and porosity) for various operating conditions.     

An Engineered Tryptophan Synthase Opens New Enzymatic Pathways to β‐Methyltryptophan and Derivatives

β‐Methyltryptophans (β‐mTrp) are precursors in the biosynthesis of bioactive natural products and are used in the synthesis of peptidomimetic‐based therapeutics. Currently β‐mTrp is produced by inefficient multistep synthetic methods. Here we demonstrate how an engineered variant of tryptophan synthase from Salmonella (StTrpS) can catalyse the efficient condensation of l ‐threonine and various indoles to generate β‐mTrp and derivatives in a single step. Although l ‐serine is the natural substrate for TrpS, targeted mutagenesis of the StTrpS active site provided a variant (βL166V) that can better accommodate l ‐Thr as a substrate. The condensation of l ‐Thr and indole proceeds with retention of configuration at both α‐ and β‐positions to give (2S,3S)‐β‐mTrp. The integration of StTrpS (βL166V) with l ‐amino acid oxidase, halogenase enzymes and palladium chemocatalysts provides access to further d ‐configured and regioselectively halogenated or arylated β‐mTrp derivatives.