MAPPING A VOLCANIC WORLD: A NEW UNDERSTANDING OF SHIELD VOLCANO MORPHOLOGY AND SPATIAL RELATIONSHIPS ON VENUS

2020 ◽  
Author(s):  
Rebecca Hahn ◽  
◽  
Paul K. Byrne
2019 ◽  
Author(s):  
Zacharias Kinney ◽  
Viraj Kirinda ◽  
Scott Hartley

<p>Higher-order structure in abiotic foldamer systems represents an important but largely unrealized goal. As one approach to this challenge, covalent assembly can be used to assemble macrocycles with foldamer subunits in well-defined spatial relationships. Such systems have previously been shown to exhibit self-sorting, new folding motifs, and dynamic stereoisomerism, yet there remain important questions about the interplay between folding and macrocyclization and the effect of structural confinement on folding behavior. Here, we explore the dynamic covalent assembly of extended <i>ortho</i>-phenylenes (hexamer and decamer) with rod-shaped linkers. Characteristic <sup>1</sup>H chemical shift differences between cyclic and acyclic systems can be compared with computational conformer libraries to determine the folding states of the macrocycles. We show that the bite angle provides a measure of the fit of an <i>o</i>-phenylene conformer within a shape-persistent macrocycle, affecting both assembly and ultimate folding behavior. For the <i>o</i>-phenylene hexamer, the bite angle and conformer stability work synergistically to direct assembly toward triangular [3+3] macrocycles of well-folded oligomers. For the decamer, the energetic accessibility of conformers with small bite angles allows [2+2] macrocycles to be formed as the predominant species. In these systems, the <i>o</i>-phenylenes are forced into unusual folding states, preferentially adopting a backbone geometry with distinct helical blocks of opposite handedness. The results show that simple geometric restrictions can be used to direct foldamers toward increasingly complex geometries.</p>


2019 ◽  
Author(s):  
Zacharias Kinney ◽  
Viraj Kirinda ◽  
Scott Hartley

<p>Higher-order structure in abiotic foldamer systems represents an important but largely unrealized goal. As one approach to this challenge, covalent assembly can be used to assemble macrocycles with foldamer subunits in well-defined spatial relationships. Such systems have previously been shown to exhibit self-sorting, new folding motifs, and dynamic stereoisomerism, yet there remain important questions about the interplay between folding and macrocyclization and the effect of structural confinement on folding behavior. Here, we explore the dynamic covalent assembly of extended <i>ortho</i>-phenylenes (hexamer and decamer) with rod-shaped linkers. Characteristic <sup>1</sup>H chemical shift differences between cyclic and acyclic systems can be compared with computational conformer libraries to determine the folding states of the macrocycles. We show that the bite angle provides a measure of the fit of an <i>o</i>-phenylene conformer within a shape-persistent macrocycle, affecting both assembly and ultimate folding behavior. For the <i>o</i>-phenylene hexamer, the bite angle and conformer stability work synergistically to direct assembly toward triangular [3+3] macrocycles of well-folded oligomers. For the decamer, the energetic accessibility of conformers with small bite angles allows [2+2] macrocycles to be formed as the predominant species. In these systems, the <i>o</i>-phenylenes are forced into unusual folding states, preferentially adopting a backbone geometry with distinct helical blocks of opposite handedness. The results show that simple geometric restrictions can be used to direct foldamers toward increasingly complex geometries.</p>


Geosciences ◽  
2021 ◽  
Vol 11 (7) ◽  
pp. 283
Author(s):  
Allan Audsley ◽  
Tom Bradwell ◽  
John Howe ◽  
John Baxter

Sub-seabed gas is commonly associated with seabed depressions known as pockmarks—the main venting sites for hydrocarbon gases to enter the water column. Sub-seabed gas accumulations are characterized by acoustically turbid or opaque zones in seismic reflection profiles, taking the form of gas blankets, curtains or plumes. How the migration of sub-seabed gas relates to the origin and distribution of pockmarks in nearshore and fjordic settings is not well understood. Using marine geophysical data from Loch Linnhe, a Scottish fjord, we show that shallow sub-seabed gas occurs predominantly within glaciomarine facies either as widespread blankets in basins or as isolated pockets. We use geospatial ‘hot-spot’ analysis conducted in ArcGIS to identify clusters of pockmarks and acoustic (sub-seabed) profile interpretation to identify the depth to gas front across the fjord. By combining these analyses, we find that the gas below most pockmarks in Loch Linnhe is between 1.4 m and 20 m deep. We anticipate that this work will help to understand the fate and mobility of sedimentary carbon in fjordic (marine) settings and advise offshore industry on the potential hazards posed by pockmarked seafloor regions even in nearshore settings.


Author(s):  
Jessica Di Salvatore ◽  
Andrea Ruggeri

Abstract How does space matter in our analyses? How can we evaluate diffusion of phenomena or interdependence among units? How biased can our analysis be if we do not consider spatial relationships? All the above questions are critical theoretical and empirical issues for political scientists belonging to several subfields from Electoral Studies to Comparative Politics, and also for International Relations. In this special issue on methods, our paper introduces political scientists to conceptualizing interdependence between units and how to empirically model these interdependencies using spatial regression. First, the paper presents the building blocks of any feature of spatial data (points, polygons, and raster) and the task of georeferencing. Second, the paper discusses what a spatial matrix (W) is, its varieties and the assumptions we make when choosing one. Third, the paper introduces how to investigate spatial clustering through visualizations (e.g. maps) as well as statistical tests (e.g. Moran's index). Fourth and finally, the paper explains how to model spatial relationships that are of substantive interest to some of our research questions. We conclude by inviting researchers to carefully consider space in their analysis and to reflect on the need, or the lack thereof, to use spatial models.


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