Mechanistic analysis of an asymmetric palladium-catalyzed conjugate addition of arylboronic acids to β-substituted cyclic enones.

An asymmetric palladium-catalyzed conjugate addition reaction of arylboronic acids to enone substrates was investigated mechanistically. Desorption electrospray ionization coupled to mass spectrometry was used to identify intermediates of the catalytic cycle and delineate differences in substrate reactivity. Our findings provide evidence for the catalytic cycle proceeding through formation of an arylpalladium(II) cation, subsequent formation of an arylpalladium-enone complex, and, ultimately, formation of the new C-C bond. Reaction monitoring in both positive and negative ion modes revealed that 4-iodophenylboronic acid formed a relatively stable trimeric species under the reaction conditions

Systems Integration Processes for NASA Ares I Crew Launch Vehicle

NASA's Exploration Initiative will require development of many new elements to constitute a robust system of systems. New launch vehicles are needed to place cargo and crew in stable Low Earth Orbit (LEO). This paper examines the systems integration processes NASA is utilizing to ensure integration and control of propulsion and nonpropulsion elements within NASA's Crew Launch Vehicle (CLV), now known as the Ares I. The objective of the Ares I is to provide the transportation capabilities to meet the Constellation Program requirements for delivering a Crew Exploration Vehicle (CEV) or other payload to LEO in support of the lunar and Mars missions. The Ares I must successfully provide this capability within cost and schedule, and with an acceptable risk approach. This paper will describe the systems engineering management processes that will be applied to assure Ares I Project success through complete and efficient technical integration. Discussion of technical review and management processes for requirements development and verification, integrated design and analysis, integrated simulation and testing, and the integration of reliability, maintainability and supportability (RMS) into the design will also be included. The Ares I Project is logically divided into elements by the major hardware groupings, and associated management, system engineering, and integration functions. The processes to be described herein are designed to integrate within these Ares I elements and among the other Constellation projects. Also discussed is launch vehicle stack integration (Ares I to CEV, and Ground and Flight Operations integration) throughout the life cycle, including integrated vehicle performance through orbital insertion, recovery of the first stage, and reentry of the upper stage. The processes for decomposing requirements to the elements and ensuring that requirements have been correctly validated, decomposed, and allocated, and that the verification requirements are properly defined to ensure that the system design meets requirements, will be discussed

Heartwood Formation and Natural Durability—A Review

This paper reviews recent literature on the formation of heartwood and on the components that affect natural durability. It includes discussion about the function of heartwood in living trees, factors influencing the natural durability of heartwood, the process of heartwood formation, and variations in heartwood quantity and quality. Heartwood formation is a regular occurrence in tree stems, and heartwood may have many different properties from sapwood, including natural decay resistance. A greater understanding of the heartwood formation process could allow control of heartwood production. Recent research involving enzymatic analyses have provided valuable insight into the biochemical processes involved in heartwood formation. Further study of the role natural durability plays in living trees would help to bring together many of the disparate strands of research relating to heartwood

Isoform-specific subcellular localization and function of protein kinase A identified by mosaic imaging of mouse brain.

Protein kinase A (PKA) plays critical roles in neuronal function that are mediated by different regulatory (R) subunits. Deficiency in either the RIβ or the RIIβ subunit results in distinct neuronal phenotypes. Although RIβ contributes to synaptic plasticity, it is the least studied isoform. Using isoform-specific antibodies, we generated high-resolution large-scale immunohistochemical mosaic images of mouse brain that provided global views of several brain regions, including the hippocampus and cerebellum. The isoforms concentrate in discrete brain regions, and we were able to zoom-in to show distinct patterns of subcellular localization. RIβ is enriched in dendrites and co-localizes with MAP2, whereas RIIβ is concentrated in axons. Using correlated light and electron microscopy, we confirmed the mitochondrial and nuclear localization of RIβ in cultured neurons. To show the functional significance of nuclear localization, we demonstrated that downregulation of RIβ, but not of RIIβ, decreased CREB phosphorylation. Our study reveals how PKA isoform specificity is defined by precise localization

Increased Abundance of the Common Raven Within the Ranges of Greater and Gunnison Sage-grouse: Influence of Anthropogenic Subsidies and Fire

The common raven (Corvus corax; raven) is native to North America and has increased in abundance, especially throughout western North America, during the last century. Human subsidies have facilitated raven dispersal into less suitable habitats and enabled these populations to maintain higher annual survival and reproduction. Concomitantly, overabundant raven populations are impacting other native at-risk species such as the greater sage-grouse (Centrocercus urophasianus) and potentially the Gunnison sage-grouse (C. minimus). Using Breeding Bird Survey data from 1995–2014, we evaluated raven count data to quantitatively describe changes in abundance and expansion into sagebrush (Artemisia spp.) ecosystems, specifically sage-grouse habitat. We focused our analyses on the 7 sage-grouse management zones (MZs) delineated across 11 western U.S. states and 2 Canadian provinces. We assessed the effects of land cover and anthropogenic disturbance on instantaneous growth rate (r) or carrying capacity (K) of ravens. Abundance of ravens in western and southeastern MZs was greater than northeastern MZs within the greater sage-grouse range. While raven abundance was lower in MZ I and II (Alberta, Canada; Dakotas, Montana, and northwestern Colorado, USA; Saskatchewan, Canada; and Wyoming, USA), raven expansion and percent increase were equivalent or greater than all other MZs. High abundance in MZ VII indicated Gunnison sage-grouse have been exposed to increased raven populations for several decades. Areas with greater electric power transmission line density had higher r; higher K was positively related to proportion of urban land cover within 25 km and burned area within 3 km and negatively related to greater distance from landfills and proportion of forest land cover within 15 km. Ravens have capitalized on human subsidies to increase abundance and expand into sagebrush ecosystems that did not historically support high raven populations. As such, managers are now faced with a new dilemma of reducing populations of a native species to benefit other native sagebrush obligate species