599 research outputs found

    Helical frontier orbitals of conjugated linear molecules

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    Compounds containing allenes, cumulenes and oligoynes (polyalkynes) have attracted attention for both their conformation and reactivity. Whilst the textbook molecular orbital description explains the general electronic and molecular structure of the cumulenes, there are anomalies in both the crystal structures and cycloaddition products involving oligoynes and allenes; the understanding of these molecules is incomplete. Through a computational study we elucidate that the frontier orbitals of the allene and oligoyne families are extended helices. These orbitals are the linear analogue to the Möbius aromatic systems, which also display non-linear π interactions. The axial chirality found in allenes and oligoynes is intimately related to the topology of the frontier orbitals, and has implications for predictions of cycloaddition pathways, structure stability and spectroscopy

    Vertical zonation of testate amoebae in the Elatia Mires, northern Greece : palaeoecological evidence for a wetland response to recent climate change or autogenic processes?

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    The Elatia Mires of northern Greece are unique ecosystems of high conservation value. The mires are climatically marginal and may be sensitive to changing hydroclimate, while northern Greece has experienced a significant increase in aridity since the late twentieth century. To investigate the impact of recent climatic change on the hydrology of the mires, the palaeoecological record was investigated from three near-surface monoliths extracted from two sites. Testate amoebae were analysed as sensitive indicators of hydrology. Results were interpreted using transfer function models to provide quantitative reconstructions of changing water table depth and pH. AMS radiocarbon dates and 210Pb suggest the peats were deposited within the last c. 50 years, but do not allow a secure chronology to be established. Results from all three profiles show a distinct shift towards a more xerophilic community particularly noted by increases in Euglypha species. Transfer function results infer a distinct lowering of water tables in this period. A hydrological response to recent climate change is a tenable hypothesis to explain this change; however other possible explanations include selective test decay, vertical zonation of living amoebae, ombrotrophication and local hydrological change. It is suggested that a peatland response to climatic change is the most probable hypothesis, showing the sensitivity of marginal peatlands to recent climatic change

    Application of MJO Simulation Diagnostics to Climate Models

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    The ability of eight climate models to simulate the Madden-Julian oscillation (MJO) is examined using diagnostics developed by the U.S. Climate Variability and Predictability (CLIVAR) MJO Working Group. Although the MJO signal has been extracted throughout the annual cycle, this study focuses on the boreal winter (November-April) behavior. Initially, maps of the mean state and variance and equatorial space-time spectra of 850-hPa zonal wind and precipitation are compared with observations. Models best represent the intraseasonal space-time spectral peak in the zonal wind compared to that of precipitation. Using the phase-space representation of the multivariate principal components (PCs), the life cycle properties of the simulated MJOs are extracted, including the ability to represent how the MJO evolves from a given subphase and the associated decay time scales. On average, the MJO decay (e-folding) time scale for all models is shorter (~20- 29 days) than observations (~31 days). All models are able to produce a leading pair of multivariate principal components that represents eastward propagation of intraseasonal wind and precipitation anomalies, although the fraction of the variance is smaller than observed for all models. In some cases, the dominant time scale of these PCs is outside of the 30-80-day band. Several key variables associated with the model's MJO are investigated, including the surface latent heat flux, boundary layer (925 hPa) moisture convergence, and the vertical structure of moisture. Low-level moisture convergence ahead (east) of convection is associated with eastward propagation in most of the models. A few models are also able to simulate the gradual moistening of the lower troposphere that precedes observed MJO convection, as well as the observed geographical difference in the vertical structure of moisture associated with the MJO. The dependence of rainfall on lower tropospheric relative humidity and the fraction of rainfall that is stratiform are also discussed, including implications these diagnostics have for MJO simulation. Based on having the most realistic intraseasonal multivariate empirical orthogonal functions, principal component power spectra, equatorial eastward propagating outgoing longwave radiation (OLR), latent heat flux, low-level moisture convergence signals, and vertical structure of moisture over the Eastern Hemisphere, the superparameterized Community Atmosphere Model (SPCAM) and the ECHAM4/Ocean Isopycnal Model (OPYC) show the best skill at representing the MJO.open1149

    Effects of coastal urbanization on salt-marsh faunal assemblages in the northern Gulf of Mexico

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    Author Posting. © American Fisheries Society, 2014. This article is posted here by permission of American Fisheries Society for personal use, not for redistribution. The definitive version was published in Marine and Coastal Fisheries: Dynamics, Management, and Ecosystem Science 6 (2014): 89-107, doi:10.1080/19425120.2014.893467.Coastal landscapes in the northern Gulf of Mexico, specifically the Mississippi coast, have undergone rapid urbanization that may impact the suitability of salt-marsh ecosystems for maintaining and regulating estuarine faunal communities. We used a landscape ecology approach to quantify the composition and configuration of salt-marsh habitats and developed surfaces at multiple spatial scales surrounding three small, first-order salt-marsh tidal creeks arrayed along a gradient of urbanization in two river-dominated estuaries. From May 3 to June 4, 2010, nekton and macroinfauna were collected weekly at all six sites. Due to the greater abundance of grass shrimp Palaemonetes spp., brown shrimp Farfantepenaeus aztecus, blue crab Callinectes sapidus, Gulf Menhaden Brevoortia patronus, and Spot Leiostomus xanthurus, tidal creeks in intact natural (IN) salt-marsh landscapes supported a nekton assemblage that was significantly different from those in partially urbanized (PU) or completely urbanized (CU) salt-marsh landscapes. However, PU landscapes still supported an abundant nekton assemblage. In addition, the results illustrated a linkage between life history traits and landscape characteristics. Resident and transient nekton species that have specific habitat requirements are more likely to be impacted in urbanized landscapes than more mobile species that are able to exploit multiple habitats. Patterns were less clear for macroinfaunal assemblages, although they were comparatively less abundant in CU salt-marsh landscapes than in either IN or PU landscapes. The low abundance or absence of several macroinfaunal taxa in CU landscapes may be viewed as an additional indicator of poor habitat quality for nekton. The observed patterns also suggested that benthic sediments in the CU salt-marsh landscapes were altered in comparison with IN or PU landscapes. The amount of developed shoreline and various metrics related to salt marsh fragmentation were important drivers of observed patterns in nekton and macroinfaunal assemblages

    Electronic structure design for nanoporous, electrically conductive zeolitic imidazolate frameworks

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    Electronic structure calculations are used to develop design rules for enhanced electrical conductivity in zeolitic imidazolate frameworks. The electrical resistivity of Co2+ based zeolitic imidazolate frameworks has previously been found to be ∼1000 times lower than that of Zn2+ based materials. The electrical conductivity of the frameworks can also be tuned by ligand molecule selection. Using density functional theory calculations, this controllable electrical conductivity is explained in terms of tuneable conduction band edge character, with calculations revealing the improved hybridisation and extended band character of the Co2+ frameworks. The improvements in the methylimidazolate frameworks are understood in terms of improved frontier orbital matching between metal and ligand. The modular tuneability and previously demonstrated facile synthesis provides a route to rational design of stable framework materials for electronic applications. By outlining these design principles we provide a route to the future development of stable, electrically conductive zeolitic imidazolate frameworks

    Notes on the Biology of an Adult Female Chimaera cubana Captured Off St. Croix, U.S. Virgin Islands

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    Within the western North Atlantic Ocean there are at least 4 genera and 5 species of chimaeroids occurring in deep waters generally associated with outer continental slopes or areas of high bathymetric relief (Didier 2002; Didier 2004). Two chimaeroids, Chimaera cubana and Hydrolagus alberti, are known to be indigenous to the Caribbean Sea in waters associated with the Greater and Lesser Antilles. While H. alberti occurs throughout the Gulf of Mexico and the Caribbean Sea, C. cubana is thought to be endemic to an area bounded by Cuba and Colombia (IUCN 2009). These two chimaeras are readily differentiated by the presence or absence of an anal fin and species–specific branching patterns of cranial lateral line canals (Didier 2004). Since the description of C. cubana by Howell–Rivero (1936), only 10 specimens have been reported in the primary literature with another 11 specimens located in museum collections (Bunkley–Williams and Williams 2004). The dearth of biological information on C. cubana led the International Union for the Conservation of Nature to recommend that “basic data be collected on all captures” (IUCN 2009)

    Introduction to “Binary Binds”: Deconstructing Sex and Gender Dichotomies in Archaeological Practice

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    YesGender archaeology has made significant strides toward deconstructing the hegemony of binary categorizations. Challenging dichotomies such as man/woman, sex/gender, and biology/culture, approaches informed by poststructuralist, feminist, and queer theories have moved beyond essentialist and universalist identity constructs to more nuanced configurations. Despite the theoretical emphasis on context, multiplicity, and fluidity, binary starting points continue to streamline the spectrum of variability that is recognized, often reproducing normative assumptions in the evidence. The contributors to this special issue confront how sex, gender, and sexuality categories condition analytical visibility, aiming to develop approaches that respond to the complexity of theory in archaeological practice. The papers push the ontological and epistemological boundaries of bodies, personhood, and archaeological possibility, challenging a priori assumptions that contain how sex, gender, and sexuality categories are constituted and related to each other. Foregrounding intersectional approaches that engage with ambiguity, variability, and difference, this special issue seeks to “de-contain” categories, assumptions, and practices from “binding” our analytical gaze toward only certain kinds of persons and knowledges, in interpretations of the past and practices in the present
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