Enantioselective organocatalysis using SOMO activation

The asymmetric alpha-addition of relatively nonpolar hydrocarbon substrates, such as allyl and aryl groups, to aldehydes and ketones remains a largely unsolved problem in organic synthesis, despite the wide potential utility of direct routes to such products. We reasoned that well-established chiral amine catalysis, which activates aldehydes toward electrophile addition by enamine formation, could be expanded to this important reaction class by applying a single-electron oxidant to create a transient radical species from the enamine. We demonstrated the concept of singly occupied molecular orbital (SOMO) activation with a highly selective alpha-allylation of aldehydes, and we here present preliminary results for enantioselective heteroarylations and cyclization/halogenation cascades.     

Photoperiod and Soil Munition Constituent Effects on Phytoaccumulation and Rhizosphere Interactions in Boreal Vegetation

Permafrost thaw is expected to alter biogeochemistry and hydrology, potentially increasing the mobility of soil constituents. Northern latitude boreal forests where permafrost thaw is occurring also experience extreme changes in day length during the growing season. As the effects of photoperiod on plant uptake of soil constituents or interactions with the rhizosphere are unknown, our objective was to determine these interactions with three plant species from different functional groups. A tree, forb, and grass common to military training ranges in this region were grown in soil spiked with or without lead, antimony, or 2,4-dinitrotoluene and grown under 16, 20, or 24 h of light. Plant biomass, soil constituent uptake, and rhizosphere bacterial communities were compared between treatments. Photoperiod had no effect on plant uptake of any soil constituent or on rhizosphere community, indicating that plants and their associated microbial communities adapted to this environment are resilient to extremes in photoperiod. Lead uptake was not significant in any plant species and had no effect on the rhizosphere. Antimony increased the percentage composition of Saprospirales in the rhizospheres of two of the three plants, indicating an interaction between this bacterial order and antimony. Antimony uptake by white spruce (Picea glauca) was considerable, with a mean concentration of 1731 mg kg^?1 in roots, while mean shoot concentration was only 155 mg kg^?1, indicating its potential to phytostabilize this heavy metal. Although antimony had the strongest impact on the rhizosphere bacterial community, it was also readily accumulated by the grass and tree.     

Investigation of isomeric transformations of chlorogenic acid in buffers and biological matrixes by ultraperformance liquid chromatography coupled with hybrid quadrupole/ion mobility/orthogonal acceleration time-of-flight mass spectrometry

Ultraperformance liquid chromatography coupled with hybrid quadrupole/ion mobility/orthogonal acceleration time-of-flight (oa-TOF) mass spectrometry (UPLC-IM-MS) was used to study the isomeric transformations of trans-5-caffeoylquinic acid, an extremely active compound present in multiple vegetables, fruits, and beverages. The UPLC/oa-TOF MS results proved that in phosphate buffer (pH 7.4), plasma, or urine sample, trans-5-caffeoylquinic acid first isomerizes to trans-4-caffeoylquinic acid and then to trans-3-caffeoylquinic acid by intramolecular acyl migration. When exposed to UV light, trans-3-, -4-, and -5-caffeoylquinic acids undergo cis/trans isomerization to form cis isomers. The isomerization was solely dependent on the pH of the matrix, as well as the incubation temperature, and was independent of metabolic enzymes. UPLC-IM-MS results revealed that a reversible cis/trans isomerization of caffeoylquinic acids could also be induced by the electric field in an electrospray source. Thus, understanding the possible role of electric field-induced isomerization of caffeoylquinic acids may help lessen the confusion between gas phase phenomena and liquid state chemistry when applying IM-MS analysis. The comprehensive understanding of caffeoylquinic acid isomerization transformations is crucial for the appropriate handling of samples and interpretation of experimental data.     

On the potential of documenting decadal-scale avifaunal change from before-and-after comparisons of museum and observational data across North America

Studies of biodiversity dynamics have been cast on either long(systematics)or short(ecology)time scales,leaving a gap in coverage for moderate time scales of de...     

Soil microbial and nutrient dynamics in a wet Arctic sedge meadow in late winter and early spring

Microbial activity is known to continue during the winter months in cold alpine and Arctic soils often resulting in high microbial biomass. Complex soil nutrient dynamics characterize the transition when soil temperatures approach and exceed 0 °C in spring. At the time of this transition in alphine soils microbial biomass declines dramatically together with soil pools of available nutrients. This pattern of change characterizes alpine soils at the winter-spring transition but whether a similar pattern occurs in Arctic soils, which are colder, is unclear. In this study amounts of microbial biomass and the availability of carbon (C), nitrogen (N) and phosphorus (P) for microbial and plant growth in wet peaty soils of an Arctic sedge meadow have been determined across the winter-spring boundary. The objective was to determine the likely causes of the decline in microbial biomass in relation to temperature change and nutrient availability. The pattern of soil temperature at depths of 5-15 cm can be divided into three phases: below −10 °C in late winter, from −7 to 0 °C for 7 weeks during a period of freeze-thaw cycles and above 0 °C in early spring. Peak microbial biomass and nutrient availability occurred early in the freeze-thaw phase. Subsequently, a steady decrease in inorganic N occurred, so that when soil temperatures rose above 0 °C, pools of inorganic nutrients in soils were very low. In contrast, amounts of microbial C and soluble organic C and N remained high until the end of the period of freeze-thaw cycles, when a sudden collapse occurred in soluble organic C and N and in phosphatase activity, followed by a crash in microbial biomass just prior to soil temperatures rising consistently above 0 °C. Following this, there was no large pulse of available nutrients, implying that competition for nutrients from roots results in the collapse of the microbial pool.     

AAHA dental care guidelines for dogs and cats

The purpose of this document is to provide guidelines for the practice of companion animal dentistry for the veterinary profession. Dental care is necessary to provide optimum health and quality of life. Diseases of the oral cavity, if left untreated, are often painful and can contribute to other local or systemic diseases. This paper includes guidelines for materials and equipment, dental cleaning and evaluation, client communication, and pet home care.     

Thrombocytopenia in Horses: 35 Cases (1989–1994)

The records of 3,952 equine patients presenting to the Veterinary Teaching Hospital at North Carolina State University College of Veterinary Medicine were evaluated to determine risk factors associated with thrombocytopenia. Of 2,346 horses from which a CBC was obtained, 35 (1.49%) were thrombocytopenic (platelet count < 75,000/μL). A reference population of 189 horses with normal platelet counts (75,000 to 300,000/μL) was also studied. Standardbred horses were at increased risk for thrombocytopenia. but age and gender were not identified as significant risk factors. Horses with infectious or inflammatory diseases were at increased risk for thrombocytopenia. The potential association of clinical and clinicopathologic factors with thrombocytopenia were assessed by reviewing a series of multiple logistic regression models. Clinical and clinicopathologic variables significantly associated with thrombocytopenia in the final model included increased PCV, increased band neutrophil count, increased total WBC, and decreased plasma protein concentration. Increased mature neutrophil count was associated with normal platelet counts. Thrombocytopenic horses were significantly more likely to die or be euthanized than were horses with normal platelet counts. J Vet Intern Med 1996;10:127–132. Copyright © 1996 by the American College of Veterinary Internal Medicine .     

Effects of salinity and temperature during incubation on hatching and development of lingcod Ophiodon elongatus Girard, embryos

The interactive effects of salinity and temperature on development and hatching success of lingcod, Ophiodon elongatus Girard, were studied by incubating eggs at four temperatures (6, 9, 12 and 15°C) and five salinities (15, 20, 25, 30 and 35 g L^?1). Hatch did not occur in any of the 15°C treatments. Degree days (°C days) to first hatch was not influenced by temperature or salinity, however, calendar days to first hatch differed significantly for temperature (P<0.0001, 61±1, 44±1 and 35±1 days for 6, 9 and 12°C respectively). Degree days to 50% (427.1±4.2) hatch was not significantly influenced by temperature but was by salinity (P=0.0324). Viable hatch (live with no deformities, 74.1±4.0%) was greatest at 9°C and 25 g L^?1 but not significantly different in the range of 20–30 g L^?1. Larval length (9.4±0.13 mm) was greatest at 9°C and 20–30 g L^?1. Temperature and salinity significantly influenced all categories of deformities with treatments at the upper (12°C and 35 g L^?1) and lower limits (6°C and 15 g L^?1) producing the greatest deformities. The optimal temperature and salinity for incubating Puget Sound lingcod eggs was found to be 9°C and 20–30 g L^?1.