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.     

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.     

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.     

Ag-ZnO catalysts for UV-photodegradation of methylene blue

High surface area Ag-ZnO catalysts have been made by flame spray pyrolysis (FSP) and characterized by X-ray diffraction (XRD), nitrogen adsorption, UV–vis spectroscopy and electron microscopy (SEM and transmission electron microscopy (TEM)) combined with energy dispersive X-ray spectroscopy (EDXS) for elemental mapping. Silver metal clusters deposited directly on ZnO nanocrystals were obtained from this process. The Ag loading (1–5 at.%) controlled the Ag cluster size from 5 to 25 nm but did not influence the ZnO crystal size. Photodegradation of 10 ppm methylene blue (MB) solution was used to evaluate the performance of these FSP-made Ag-ZnO and was compared to wet-made Ag-ZnO and reference titania photocatalysts. The rate of photodegradation was optimal for Ag loading around 3 at.%. The best photocatalytic performance was exhibited by flame-made Ag-ZnO produced at the longest high-temperature residence times having high crystallinity as determined by XRD and UV–vis.     

Diterpene resin acids: Major active principles in tall oil against Variegated cutworm,Peridroma saucia (Lepidoptera: Noctuidae)

Tall oil, a by-product of the kraft process for pulping softwood, has been shown to have insecticidal properties. In the present study, the active principles in tall oil against the variegated cutworm,Peridroma saucia Hübner, were investigated. GC-MS analysis showed that abietic, dehydroabietic, and isopimaric acids were major resin acid components of crude tall oil and depitched tall oil. When crude tall oil samples of differing resin acid composition were incorporated into artificial diet at a concentration of 2.0% fresh weight, they suppressed larval growth by 45–60% compared to controls. This suppression was significantly (P0.05) correlated with the equivalent contents of abietic, dehydroabietic, isopimaric, and total resin acids. These results were also evident from a diet choice test, showing that the second-instar larvae obviously selected diets with low levels of resin acids when different diets were randomly arranged in a Petri dish. Bioassays with pure resin acids (abietic, dehydroabietic, and isopimaric acids) demonstrated that all individual chemicals have similar bioactivity against this insect. Comparison of the bioactivities of depitched tall oil and an equivalent mixture of pure resin acids in thePeridroma chronic growth bioassay indicated that pure resin acids and depitched tall oil share a common mode of action to this insect. This study confirms that resin acids are major active principles in tall oil against the variegated cutworm, but other chemicals likely also contribute to the bioactivity of tall oil.     

Analysis of the Insect OS-D-Like Gene Family

Insect OS-D-like proteins, also known as chemosensory (CSP) or sensory appendage proteins (SAP), are broadly expressed in various insect tissues, where they are thought to bind short to medium chain length fatty acids and their derivatives. Although their specific function remains uncertain, OS-D-like members have been isolated from sensory organs (including the sensillum lymph in some cases), and a role in olfaction similar to that of the insect odorant binding proteins (OBP) has been suggested for some. We have identified 15 new OS-D-like sequences: four from cDNA clones described herein and 11 from sequence databases. The os-d-like genes from the Anopheles gambiae, Apis mellifera, Drosophila melanogaster, and Drosophila pseudoobscura genomes typically have single, small introns with a conserved splice site. Together with all family members entered on GenBank, a total of 70 OS-D-like proteins, representing the insect orders Diptera, Dictyoptera, Hymenoptera, Lepidoptera, Orthoptera, and Phasmatodea, were analyzed. A neighbor joining distance phenogram identified several protein similarity classes that were characterized by highly conserved sequence motifs, including (A) N-terminal YTTKYDN(V/I)(N/D)(L/V)DEIL, (B) central DGKELKXX(I/L)PDAL, and (C) C-terminal KYDP. In contrast, three similarity classes were characterized by their diversion from these conserved motifs. The functional importance of conserved amino acid residues is discussed in relation to the crystal and NMR structures of MbraCSPA6.     

The role of fats and oils in cosmetics

The earliest emollients in the history of cosmetics were the naturally occurring animal fats and vegetable oils. These provided soothing and smoothing action on the skin and grooming effects on head and beard hair. For the most part, odor problems limited the interest in oils derived from fish. With the increasing sophistication of users and increasing understanding of the technology of these materials, the short-comings of natural fats and oils were overcome in several ways: (a) increased stability through use of antioxidants; (b) reduced odor through improved processing; (c) improved stability and diversification through chemical modification; (d) increased diversity through preparation of derivatives, and (e) substitution of mineral oil. Today the most important single cosmetic use of an unmodified natural fat or oil is that of castor oil as the base for lipsticks. Other unmodified oils have largely minor specialty uses, particularly in higher-priced cosmetics. These include almond oil, apricot kernel oil, sesame oil, safflower oil, wheat germ oil, avocado oil, turtle oil and mink oil. Cocoa butter is used to some extent in suntan products. Reconstituted fractionated coconut oil is widely used. Polyglycerol esters of fatty acids are increasing in importance. Hydrogenation has produced stable oils useful in cosmetics. Alkyl esters and monoglycerol esters of fatty acids offer a wider range of properties than the original oils. Improvements in the naturally occurring fats and oils have made it possible for them to compete in some characteristics, and current interest in “natural” cosmetics may turn the attention of the cosmetic chemist back to improved versions of the classical raw materials. One of five papers in the symposium “Fats and Oils in Cosmetics and Pharmaceuticals,” presented at the AOCS Meeting, Atlantic City, October 1971.     

Fundamentals of bitumen coking processes analogous to granulations: A critical review

A number of coking processes use hot particles to heat liquid bitumen or petroleum residue to cause cracking reactions. These particles may be mineral or coke solids. Interactions of these particles, in fluid beds, moving beds and other types of contactors, are governed by the liquid films on the particle surfaces. This paper explores the analogy between granulation and coking, and suggests that the key relationships that will govern the behavior of wet particles in coking processes are the Stokes number of the particles, the thickness or the liquid films, and the diameter and surface roughness of the particles. The implications for distribution of liquid feed in the reactor, fouling, and defluidization or bogging are discussed. This analysis suggests experiments that can be performed under non‐reactive conditions with scaled variables in order to study phenomena that cannot be observed in situ in high‐temperature cracking processes.