Synthesis and Study of Linear and Cyclic Polycyclopentadienones and Polypheylenes

Polyaromatic hydrocarbons (PAH) are useful molecules for supramolecular assemblies and nanoscale electronics materials. Due to their high degree of symmetry and lack of heteroatoms characterization is fairly simple and calculated properties very closely match experimental values. By utilizing a controlled, stepwise synthesis, which enables the regioselective incorporation of solubilizing side chains and electron donating or withdrawing groups, we were able to access many novel PAHs of various shapes and sizes. Using an unprecedented asymmetric protected alcohol-benzyl bromide Collman coupling strategy we have accessed linear oligocyclopentadienones and oligophenylenes not accessible through current methodology. Monomers of these two classes were studied both spectroscopically and computationally in order to fully characterize their electronic structure and see how perturbation of the PAH scaffold affected their respective molecular orbitals. Using a harsher unsymmetrical carbonylative coupling of α,α\u27-dibromoxylene we were able to access the two previously unknown low molecular weight polymers: Poly(para-phenylene)(2-isocyano-2-tosylpropane-1,3-diyl) (PPIT), and Poly(paraphenylene)( 2-oxopropane-1,3-diyl) (PPOD). PPIT and PPOD were demonstrated to be possible precursors of high molecular weight polycyclopentadienones and polyphenylenes. Small macrocycles of these polymers were also produced through the same methodology at high dilution. Conversion of the polymers and oligomers to linear and cyclic polycyclopentadienones and polyphenylenes has been demonstrated in two prototypic examples. While universal methodology for larger oligomers and polymers is still under study, we believe the ultimate goal of discrete isomer carbon nanotubes and linear graphite to be possible due in part by the work reported in this thesis

Making Connections:John Darwin and his Histories of Empire

John Darwin and his Histories of Empir

Tertiary halo and tertiary background in the low luminosity experimental insertion IR8 of the LHC

In our report we present the results for numerical simulation of tertiary halo and tertiary background in the LHC. We study the case of the proton losses in the betatron cleaning insertion IR7 with the subsequent tertiary halo generation in the downstream experimental insertion IR8. We analyze the formation of tertiary background in the experimental area of the IR8 and evaluate the performance of the machine-detector interface shielding with respect to this source of the background. The results obtained are compared with the previous estimates of the machine-induced background in the low luminosity insertions of the LHC, and the balance between different sources of the background is discussed

Intrusion of warm Bering/Chukchi waters onto the shelf in the western Beaufort Sea

Author Posting. © American Geophysical Union, 2009. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 114 (2009): C00A11, doi:10.1029/2008JC004870.Wind-driven changes in the path of warm Bering/Chukchi waters carried by the Alaska Coastal Current (ACC) through Barrow Canyon during late summer are described from high-resolution hydrography, acoustic Doppler current profiler–measured currents, and satellite-measured sea surface temperature imagery acquired from mid-August to mid-September 2005–2007 near Barrow, Alaska. Numerical simulations are used to provide a multidecadal context for these observational data. Four generalized wind regimes and associated circulation states are identified. When winds are from the east or east-southeast, the ACC jet tends to be relatively strong and flows adjacent to the shelf break along the southern flank of Barrow Canyon. These easterly winds drive inner shelf currents northwestward along the Alaskan Beaufort coast where they oppose significant eastward intrusions of warm water from Barrow Canyon onto the shelf. Because these easterly winds promote sea level set down over the Beaufort shelf and upwelling along the Beaufort slope, the ACC jet necessarily becomes weaker, broader, and displaced seaward from the Beaufort shelf break upon exiting Barrow Canyon. Winds from the northeast promote separation of the ACC from the southern flank of Barrow Canyon and establish an up-canyon current along the southern flank that is fed in part by waters from the western Beaufort shelf. When winds are weak or from the southwest, warm Bering/Chukchi waters from Barrow Canyon intrude onto the western Beaufort shelf.This work was supported in 2005 and 2006 by NSF grants OPP-0436131 and OPP-0436166. In 2007, this work received support through Woods Hole Oceanographic Institution- NOAA Cooperative Institute for Climate and Ocean Research Cooperative Agreement NA17RJ1223 and University of Alaska Fairbanks-NOAA Cooperative Institute for Arctic Research Cooperative Agreement NA17RJ1224. Additional support was provided by the James M. and Ruth P. Clark Arctic Research Initiative Fund at the Woods Hole Oceanographic Institution

Homologous and heterologous desensitization of guanylyl cyclase-B signaling in GH3 somatolactotropes

The guanylyl cyclases, GC-A and GC-B, are selective receptors for atrial and C-type natriuretic peptides (ANP and CNP, respectively). In the anterior pituitary, CNP and GC-B are major regulators of cGMP production in gonadotropes and yet mouse models of disrupted CNP and GC-B indicate a potential role in growth hormone secretion. In the current study, we investigate the molecular and pharmacological properties of the CNP/GC-B system in somatotrope lineage cells. Primary rat pituitary and GH3 somatolactotropes expressed functional GC-A and GC-B receptors that had similar EC50 properties in terms of cGMP production. Interestingly, GC-B signaling underwent rapid homologous desensitization in a protein phosphatase 2A (PP2A)-dependent manner. Chronic exposure to either CNP or ANP caused a significant down-regulation of both GC-A- and GC-B-dependent cGMP accumulation in a ligand-specific manner. However, this down-regulation was not accompanied by alterations in the sub-cellular localization of these receptors. Heterologous desensitization of GC-B signaling occurred in GH3 cells following exposure to either sphingosine-1-phosphate or thyrotrophin-releasing hormone (TRH). This heterologous desensitization was protein kinase C (PKC)-dependent, as pre-treatment with GF109203X prevented the effect of TRH on CNP/GC-B signaling. Collectively, these data indicate common and distinct properties of particulate guanylyl cyclase receptors in somatotropes and reveal that independent mechanisms of homologous and heterologous desensitization occur involving either PP2A or PKC. Guanylyl cyclase receptors thus represent potential novel therapeutic targets for treating growth-hormone-associated disorders

Revisiting the proposed planetary system orbiting the eclipsing polar HU Aquarii

It has recently been proposed, on the basis of eclipse-timing data, that the eclipsing polar cataclysmic variable HU Aquarii is host to at least two giant planets. However, that result has been called into question based upon the dynamical stability of the proposed planets. In this work, we present a detailed re-analysis of all eclipse timing data available for the HU Aquarii system, making use of standard techniques used to fit orbits to radial-velocity data. We find that the eclipse timings can be used to obtain a two-planet solution that does not require the presence of additional bodies within the system. We then perform a highly detailed dynamical analysis of the proposed planetary system. We show that the improved orbital parameters we have derived correspond to planets that are dynamically unstable on unfeasibly short timescales (of order 10^4 years or less). Given these results, we discuss briefly how the observed signal might in fact be the result of the intrinsic properties of the eclipsing polar, rather than being evidence of dynamically improbable planets. Taken in concert, our results highlight the need for caution in interpreting such timing variations as being planetary in nature.Comment: Accepted for publication in MNRA