Selectively fluorinated analogs reveal differential olfactory reception and inactivation of green leaf volatiles in insects

The role of the alkyl terminus of green leaf volatile (GLV) molecules in olfactory reception and inactivation was examined in three diverse insect species: the beet armyworm,Spodoptera exigua (Lepidoptera); the Colorado potato beetle,Leptinotarsa decemlineata (Coleoptera); and the desert locust,Schistocerca gregaria (Orthoptera), using selectively fluorinated analogs of GLVs and electroantennograms (EAGs). When only the magnitude of the depolarization of the EAG is considered (a measure of reception), the order of effectiveness was 1-hexanol (6:OH)=(Z)-3-6:OH > 5,5,6,6,6-pentafluoro-(Z)-3-6:OH =5,5-difluoro-(Z)-3-6:OH 5,5,6,6,6-pentafluoro-6: OH. Percent recovery of the EAG (a measure of inactivation) was greater for the pentafluoro-(Z)-3-6: OH analog than for the difluoro-(Z)-3-6: OH analog. Our results show that the alkyl end of GLV molecules plays an important role not only in reception, but also inactivation processes in insect olfaction. Furthermore, specificities of these two processes may differ.Research conducted by J.C.D. while on an ARS Fellowship at IPO-DLO.     

Sterol composition of the phytolaccaceae and closely related families

Total sterols were analyzed from 28 species of Phytolaccaceae and from 29 species of closely related families—Basellaceae, Portulaccaceae, Molluginaceae, and Stegnospermataceae. Eighteen of twenty-eight species of Phytolaccaceae contained dominant Δ⁷-sterols while six species had dominant Δ⁵-sterols. Three species had dominant Δ⁰-sterols. Sterol composition strongly reflected taxonomic position. Nineteen of twenty-nine species from Basellaceae, Portulaccaceae, Molluginaceae, and Stegnospermataceae contained dominant Δ⁷-sterols while ten species contained dominant Δ⁵-sterols. Until recently Δ⁷-sterols were considered rare in higher plants. It appears that a large number of species in the order Caryophyllales contain primarily Δ⁷-sterols.     

Developments in the continuous galvanizing of steel

The performance history of galvanized steels, particularly in the automotive industry, has heightened demand for both hot-dip galvanized and electrogalvanized products. Such marketability has led to the commissioning of several new galvanizing lines in recent years. Still, for this timehonored coating process to remain competitive, researchers are investigating methods to improve surface appearance, coating uniformity, corrosion resistance and cost effectiveness.     

Electrochemical hydrogen pumping using a high-temperature polybenzimidazole (PBI) membrane

Electrochemical hydrogen pumping using a high-temperature (>100 °C) polybenzimidazole (PBI) membrane was demonstrated under non-humidified and humidified conditions at ambient pressures. Relatively low voltages were required to operate the pump over a wide range of hydrogen flow rates. The advantages of the high-temperature capability were shown by operating the pump on reformate feed gas mixtures containing various amounts of CO and CO₂. Gas purity measurements on the cathode gas product were conducted and significant reductions in gas impurities were detected. The applicability of the PBI membrane for electrochemical hydrogen pumping and its durability under typical operating conditions were established with tests that lasted for nearly 4000 h.     

A band-ratio algorithm for retrieving open-lake chlorophyll values from satellite observations of the Great Lakes

The U.S. Environmental Protection Agency's Great Lakes National Program Office (GLNPO) has collected water quality data from the five Great Lakes annually since 1993. We used the GLNPO observations made since 2002 along with coincident measurements made by the Sea-viewing Wide Field-of-View Sensor (SeaWiFS) and the Moderate-resolution Imaging Spectroradiometer (MODIS) to develop a new band-ratio algorithm for estimating chlorophyll concentrations in the Great Lakes from satellite observations. The new algorithm is based on a third-order polynomial model using the same maximum band ratios employed in the standard NASA algorithms (OC4 for SeaWiFS and OC3M for MODIS). The sensor-specific coefficients for the new algorithm were obtained by fitting the relationship to several hundred matched field and satellite observations. Although there are some seasonal variations in some lakes, the relationship between the observed chlorophyll values and those modeled using the new coefficients is fairly stable from lake to lake and across years. The accuracy of the satellite chlorophyll estimates derived from the new algorithm was improved substantially relative both to the standard NASA retrievals and to previously published algorithms tuned to individual lakes. Monte-Carlo fits to randomly selected subsets of the observations allowed us to estimate the uncertainty associated with the retrievals purely as a function of the satellite data. Our results provide, for the first time, a single simple band ratio method for retrieving chlorophyll concentrations in the offshore “open” waters of the Great Lakes from satellite observations.     

Relative abundance,age structure,and body size in mudpuppy populations in southwestern Ontario

Little is known of mudpuppy (Necturus maculosus) population structure and ecology; some populations in the Great Lakes are thought to be in decline. Mudpuppies are the obligate hosts for the mudpuppy mussel (Simpsonaias ambigua), a species that is endangered in Canada and in many Great Lakes states. We surveyed mudpuppies from the Sydenham River, the only known Canadian locality of the mudpuppy mussel, in order to generate information on relative density, deformity rates and population age/size structure and used this information to compare them to known mudpuppy populations from Great Lakes sites in the Detroit River, Lake St. Clair and Long Point in Lake Erie. Deformity rates were elevated at some sites in the Sydenham River. The relative density of mudpuppies in the Sydenham River was lower than that of other Great Lakes sites and their age was skewed towards younger individuals. Although at lower densities than at other Great Lakes sites, the mudpuppy population in the Sydenham River appears stable and is showing signs of recruitment which bodes well for the future of the mudpuppy mussel population of the river.     

The Development of Alkoxide-Directed Metallacycle-Mediated Annulative Cross-Coupling Chemistry

Alkoxide-directed metallacycle-mediated cross-coupling is a rapidly growing area of reaction methodology in organic chemistry. Over the last decade, developments have resulted in more than thirty new and highly selective intermolecular (or “convergent”) C−C bond-forming reactions that have established powerful retrosynthetic relationships in stereoselective synthesis. While early studies were focused on developing transformations that forge a single C−C bond by way of a functionalized and unsaturated metallacyclopentane intermediate, recent advances mark the ability to employ this organometallic intermediate in additional stereoselective transformations. Among these more advanced coupling processes, those that embrace the metallacycle in subsequent [4+2] chemistry have resulted in the realization of a number of highly selective annulative cross-coupling reactions that deliver densely functionalized and angularly substituted carbocycles. This review discusses the early development of this chemistry, recent advances in reaction methodology, and shares a glimpse of the power of these processes in natural product synthesis.