Atom transfer mechanisms in oxidation processes

The emphasis placed on electron transfer in connection with oxidation reactions has often resulted in these processes being considered as a group apart from the main class of chemical reactions. Although some oxidations, for example certain exchange reactions between ions in solution, can be reasonably described as electron transfer processes, there are very many other oxidations, whose mechanisms are much better described in the familiar terms of modern organic chemistry.The use of isotopes as tracers has shown, that many oxidations proceed with transfer of atoms or groups from oxidant to reductant andvice versa; the use of the kinetic isotope effect has shown that such transfer is seldom an incidental process, but is almost always a part of the slow step of the reaction. In this paper, oxidations involving the transfer of such species as oxygen atoms, hydride ions, hydrogen atoms, chlorine atoms, and hydroxyl radicals are discussed in terms of mechanism. An attempt is made to show that a graded series of mechanisms is possible ranging from what appear to be pure electron transfer processes at one end to certain atom transfer processes at the other. The latter group belong, in fact, in the familiar realm of ordinary chemical raactions, in which strong bonds are being broken and formed in the activated complex.Contribution from Department of Chemistry, University of British Columbia, Vancouver. — Presented at the Organic Chemistry Symposium of the Chemical Institute of Canada, Ottawa, Dec. 8–9, 1958.     

Atypical mast cell degranulation and focal hydropic degeneration of venular endothelium in diffuse fibrosing alveolitis

Atypical scroll-like and tubular degranulation of mast cells closely associated with focal endothelial hydropic degeneration is reported in human lung from 4 patients with diffuse fibrosing alveolitis in which the predominant abnormality was hyperplasia and desquamation of type 2 pneumocytes.     

Plutonium-based superconductivity with a transition temperature above 18 K

Plutonium is a metal of both technological relevance and fundamental scientific interest. Nevertheless, the electronic structure of plutonium, which directly influences its metallurgical properties, is poorly understood. For example, plutonium's 5f electrons are poised on the border between localized and itinerant, and their theoretical treatment pushes the limits of current electronic structure calculations. Here we extend the range of complexity exhibited by plutonium with the discovery of superconductivity in PuCoGa5. We argue that the observed superconductivity results directly from plutonium's anomalous electronic properties and as such serves as a bridge between two classes of spin-fluctuation-mediated superconductors: the known heavy-fermion superconductors and the high-T(c) copper oxides. We suggest that the mechanism of superconductivity is unconventional; seen in that context, the fact that the transition temperature, T(c) approximately 18.5 K, is an order of magnitude greater than the maximum seen in the U- and Ce-based heavy-fermion systems may be natural. The large critical current displayed by PuCoGa5, which comes from radiation-induced self damage that creates pinning centres, would be of technological importance for applied superconductivity if the hazardous material plutonium were not a constituent.     

Drumming behavior and life history notes of a high-altitude Colorado population of the stonefly Isoperla petersoni Needham

Late instar nymphs and adults of a Colorado Hudsonian zone population of Isoperla petersoni Needham and Christenson were studied during the summer and early fall months of 1998, when stream temperature ranged from 3.3° C to 8.9° C. Early and middle instar nymphs were absent from July to October, and nymphs attained maximum size in mid-August during the 2nd week of adult field presence, suggesting a univoltine-slow life cycle. Nymphs were carnivorous and fed primarily on chironomid larvae. Adults were present from August to mid-October, with peak numbers of adult males and females occurring in mid-September and late September, respectively. Fecundity of field-collected females averaged 94.1 ± 45.15 eggs per female in September ( N = 81) and decreased to 85.2 ± 57.6 in October ( N = 12). Drumming duets were 2-way (male-female), and female answers followed male calls (nonoverlapped) or began before completion of the male call (overlapped). Male calls averaged 11.1 ± 2.09 beats and female answers averaged 6.2 ± 2.99, with mean intervals of 118 and 58 ms, respectively. The average number of female answer beats increased from 5.3 ± 2.56 when duets were nonoverlapped, to 6.6 ± 3.08 when overlapped.     

Breeding populations of Swainson's Hawks, Red-Tailed Hawks, and Golden Eagles in north central Oregon: 1975-1982 and 1999

Populations of breeding Swainson's Hawks ( Buteo swainsoni ), Red-tailed Hawks ( B. jamaicensis ), and Golden Eagles ( Aquila chrysaetos ) present in 1999 were compared with populations present between 1975 and 1982 at a 129-km 2 site in north central Oregon. Populations of Red-tailed Hawks and Golden Eagles remained unchanged, but the number of Swainson's Hawks pairs increased from 15 to 17. In 1999 Golden Eagles used nests occupied between 1975 and 1982, and 7 of 31 pairs of Red-tailed Hawks used nests occupied in earlier years. No Swainson's Hawks nested in trees occupied earlier. Few changes in territorial boundaries were detected.     

Beaver herbivory of willow under two flow regimes: a comparative study on the Green and Yampa rivers

The effect of flow regulation on plant-herbivore ecology has received very little attention, despite the fact that flow regulation can alter both plant and animal abundance and environmental factors that mediate interactions between them. To determine how regulated flows have impacted beaver ( Castor Canadensis ) and sandbar willow ( Salix exigua ) ecology, we first quantified the abundance and mapped the spatial distribution of sandbar willow on alluvial sections of the flow-regulated Green River and free-flowing Yampa River in northwestern Colorado. We then established 16 and 15 plots (1 m x 2.7 m) in patches of willow on the Green and Yampa Rivers, respectively, to determine whether rates of beaver herbivory of willow differed between rivers (Green versus Yampa River), seasons (fall-winter versus spring-summer), and years (spring 1998-spring 1999 versus spring 1999-spring 2000). Areal extent of willow was similar on each river, but Green River willow patches were smaller and more numerous. Beavers cut more stems during fall and winter than spring and summer and cut over 6 times more stems (percentage basis) on the Green River than on the Yampa River. We attribute the between-river difference in herbivory to higher availability of willow, greater beaver density, and lower availability of young Fremont cottonwood ( Populus deltoids subsp. wislizenii ; an alternative food source) on the Green River. Flow regulation increased willow availability to beaver by promoting the formation of island patches that are continuously adjacent to water and feature a perimeter with a relatively high proportion of willow interfacing with water.     

Vegetation response to fire and postburn seeding treatments in juniper woodlands of the Grand Staircase-Escalante National Monument, Utah

We compared 3 naturally ignited burns with unburned sites in the Grand Staircase-Escalante National Monument. Each burn site was restored with native and nonnative seed mixes, restored with native seeds only, or regenerated naturally. In general, burned sites had significantly lower native species richness (1.8 vs. 2.9 species), native species cover (11% vs. 22.5%), and soil crust cover (4.1% vs. 15%) than unburned sites. Most burned plots, seeded or not, had significantly higher average nonnative species richness and cover and lower average native species richness and cover than unburned sites. Regression tree analyses suggest site variation was equally important to rehabilitation results as seeding treatments. Low native species richness and cover, high soil C, and low cover of biological soil crusts may facilitate increased nonnative species richness and cover. Our study also found that unburned sites in the region had equally high cover of nonnative species compared with the rest of the Monument. Cheatgrass ( Bromus tectorum ) dominated both burned and unburned sites. Despite the invasion of cheatgrass, unburned sites still maintain higher native species richness; however, the high cover of cheatgrass may increase fire frequency, further reduce native species richness and cover, and ultimately change vegetation composition in juniper woodlands.