Correlation of reactivity with chemical structure: Thermal hydrogenation of gas oils

The relationship between chemical structure and reactivity for thermal hydroprocessing was studied for five gas oils derived from Alberta bitumens. Chemical structure was characterized by combining data from ¹ H and ¹³ C nuclear magnetic resonance spectroscopy, class fractionation, and elemental analysis to calculate structural parameters. Thermal hydrotreating was performed in a continuous-flow stirred reactor at 420 and 440°C, 13.9 MPa hydrogen pressure, and 1.5 h¹ LHSV. Conversion of the 343–525°C boiling fraction of the gas oils was correlated with the concentration of naphthenic methylene groups in the feed. Formation of methane and ethane was dependent on the degree of condensation of the aromatic rings in the feed oils. Thermal desulfurization was highly correlated with the amount of saturates in the feed, and the aromaticity of the resin fraction. Hydrogen consumption increased with the aromaticity of the gas oil…     

Dynamics of ion beam modification of polymer films

Thin polymer films were irradiated in a high vacuum environment with energetic (～2 MeV) ions. The emitted molecular species were studied with a quadrupole mass spectrometer during bombardment. The emitted species are predominantly small molecules. The efficiency of emission depends strongly upon the electronic energy loss of the incident ions in the film and, hence, upon the velocity and atomic number of the incident ion. The emission efficiency of all species decreases with increasing damage in the film. By pulsing the ion beam, the time dependence of irradiation induced emission of molecular species from the films has been studied. Emission delays of hundreds of milliseconds are observed in some cases. These delays are found to depend upon the emitted species as well as the host film and seem to be associated with diffusion of the species in the films.     

Reactions on Single-Crystal Metal Surfaces Studied with Scanning Tunneling Microscopy

A review is given of scanning tunneling microscopy (STM) studies of reactions between different chemical species on metal surfaces. Results presented for a variety of systems show that STM can give unique insight at the atomic level into the mechanistic details of surface reactions and decomposition of molecules. This is illustated with a number of examples of reactions occuring on single-crystal metal surfaces, such as Ni(110), Cu(110), Ag (110), Rh (110), and Pt(111). The ability of the local STM probe to study the influence of defect sites on reactivity is highlighted, and similarities and differences in reactivity of different systems are discussed. Finally, the application of STM to enhance reactivity via tip interactions is addressed.     

A generalist herbivore in a specialist mode Metabolic,sequestrative, and defensive consequences

Adults of a generalist herbivore, the lubber grasshopper,Romalea guttata, can be converted to functional specialists by feeding them exclusively on catnip,Nepeta cataria. No obvious adverse effects on adult development resulted from this enforced monophagy. Notwithstanding the fact thatR. guttata has had no coevolutionary relationship with this Eurasian mint, it readily sequesters compounds that are identical to or derived from the terpenoid lactones that are characteristic ofN. cataria. R. guttata appears to both biomagnify minor allelochemicals and to sequester metabolites of theNepeta terpenes in its paired defensive glands. The levels of autogenously produced phenolics are not affected by feeding onN. cataria and the defensive secretions of catnip-fed grasshoppers are more repellent to ants than those of wild-fed acridids. Metabolites of theN. cataria monoterpenes are sequestered in the defensive glands when catnip is added to the natural diet ofR. guttata. The ability of a generalist,R. guttata, to facilely bioaccumulate a potpourri of foreign allelochemicals when feeding in a specialist mode is analyzed in terms of its biochemical, physiological, and functional significance. Sequestration is examined as a response to the enteric effronteries represented by the phytochemicals that can be characteristic of the overload in a monophagous diet.     

The influence of soil properties on the effectiveness of phenylphosphorodiamidate (PPD) in reducing ammonia volatilization from surface applied urea

Urea can be an inefficient N source due to rapid hydrolysis by soil urease leading to NH₃ volatilization. The current study investigated the effect of the urease inhibitor phenylphosphorodiamidate (PPD) incorporated at two concentrations (0.5% and 1% w/w) within the fertilizer granule on NH₃ volatilization from surface applied urea. The daily rates of NH₃ loss from 20 soils of widely differing properties from Northern Ireland were measured over 14 days using ventilated enclosures under simulated spring conditions. Cumulative loss rates were calculated and fitted to a logistic model from which total NH₃ loss (Amax) and the time to maximum rate of loss (Tmax) were determined. Stepwise multiple linear regression analysis related the effectiveness of PPD in reducing NH₃ volatilization from urea to soil properties.The total cumulative loss of ammonia from unamended urea varied from 0.37 to 29.2% depending on soil type. Ammonia volatilization appeared to be greatest on a soil with a high pH (R² = 0.65), a low titratable acidity (TA) (R² = 0.63) and a soil that was drying out (R² = 0.50). Soil pH was negatively correlated with TA (r = –0.826, P < 0.001) suggesting that soils with a low TA may have received recent lime. Including cation exchange capacity (CEC) and % N as well as pH-KCl in the multiple linear regression equation explained 86% of the variance.The effectiveness of PPD in reducing Amax varied between 0% to 91% depending on soil type, the average over all 20 soils being 30 and 36% for 0.5% and 1% PPD respectively. The most important soil properties influencing the effectiveness of the urease inhibitor were soil pH-H₂O and TA accounting for 33% and 29% of the variance respectively. PPD was less effective on a soil with a high pH and low TA. These were the soil conditions that led to high NH₃ volatilization from unamended urea and may explain why PPD had limited success in reducing ammonia loss on these soils. Multiple linear regression analysis indicated that 75% of the variation in the % inhibition of NH₃ loss by PPD could be significantly accounted for by pH-H₂O, initial soil NO ₃ ^- -N concentration, % moisture content and % moisture loss.The delay in Tmax by PPD ranged from 0.19 to 7.93 days, the average over all 20 soils being 2.5 and 2.8 days for 0.5% and 1% PPD respectively. TA, % moisture content, urease activity and CEC were soil properties that significantly explained 83% of the variation in the % delay in Tmax by PPD in multiple linear regression analysis. However, none of these soil properties were significant on their own. As urea hydrolysis occurs rapidly in soil, delaying Tmax under field conditions would increase the chance of rain falling to move the urea below the soil surface and reduce NH₃ volatilization. A urease inhibitor should be more effective than PPD on soils with a high pH and low TA to be successful in reducing high NH₃ losses.     

Occurrence of wax esters in the tissues of the organge roughy (Hoplostethus atlanticus)

The skin, skeleton and a fat-filled swim bladder of the orange roughy (Hoplostethus atlanticus) each contained greater than 20% lipid by wet weight which was almost entirely wax esters. These had carbon numbers of 34–40 consistent with the major fatty acid being 18∶1 and the major fatty alcohols being 16∶0, 18∶1, 20∶1 and 22∶1. In contrast, the liver and the roe contained appreciable quantities of glycerolipids with 18∶1 and 22∶6 as the major fatty acids.     

Implicit Bayesian Inference Using Option Prices

Abstract. A Bayesian approach to option pricing is presented in which posterior inference about the underlying returns process is conducted implicitly via observed option prices. A range of models allowing for conditional leptokurtosis, skewness and time‐varying volatility in returns are considered, with posterior parameter distributions and model probabilities backed out from the option prices. Models are ranked according to several criteria, including out‐of‐sample predictive and hedging performance. The methodology accommodates heteroscedasticity and autocorrelation in the option pricing errors, as well as regime shifts across contract groups. The method is applied to intraday option price data on the S&P500 stock index for 1995. While the results provide support for models that accommodate leptokurtosis and skewness, no one model dominates when all criteria are considered.     

Structural–Property Relations in a Reduced and Internally Biased Oxide Wafer (RAINBOW) Actuator Material

Reduced and internally biased oxide wafer (RAINBOW) actuators are fabricated by a controlled reduction of Pb(Zr, Ti)O₃-based piezoelectric material. The reduction process results in a conductive layer composed of an interconnected metallic lead phase and refractory oxides (ZrTiO₄, ZrO₂, La₂O₃, etc.). The nature of the reduction is discovered to be the result of a complex volume change leading to a nanoscale interconnected metallic structure. The distribution of phases within the cermet vary within the thickness of the wafer. Within the piezoelectric ceramic phase, the reduction process modifies the grain-boundary structure to give two distinct types of fracture: transgranular and intergranular. The complexed microstructures of the RAINBOW actuator materials are discussed in relation to their dielectric and piezoelectric properties.     

Ozone Treatment of Surface Water to Provide High Quality Cooling Water and Process Water

The characteristic feature of this cooling tower water treatment is the intermittent addition of ozone for several days.