54 research outputs found

    Observations of tidal variability on the New England shelf

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    Author Posting. © American Geophysical Union, 2004. 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 109 (2004): C06010, doi:10.1029/2003JC001972.Observations from the Coastal Mixing and Optics experiment moored array, deployed from August 1996 through June 1997, are used to describe barotropic and baroclinic tidal variability over the New England shelf. The dominant M 2 tidal elevations decrease toward the northeast to a minimum over the Nantucket shoals (about 34 cm), and barotropic tidal current amplitudes increase strongly toward the northeast to a maximum over the shoals (about 35 cm s−1). Estimates of the depth-averaged M 2 momentum balance indicate that tidal dynamics are linear, and along-shelf pressure gradients are as large as cross-shelf pressure gradients. In addition, tidal current ellipses are weakly polarized, confirming that the dynamics are more complex than simple plane waves. The vertical structure of the M 2 currents decreases in amplitude and phase (phase lead near bottom) over the bottom 20 m. The M 2 momentum deficit near the bottom approximately matches direct covariance estimates of stress, confirming the effects of stress on current structure in the tidally driven bottom boundary layer. Baroclinic current variability at tidal frequencies is small (2 cm s−1 amplitude), with a predominantly mode 1 vertical structure. High-frequency (approaching the buoyancy frequency) internal solitons are observed following the pycnocline. The internal solitons switch from waves of depression to waves of elevation when the depth of maximum stratification is deeper than half the water column depth. Both low-mode baroclinic tidal and high-frequency internal wave energy decrease linearly with bottom depth across the shelf.Funding for the CMO experiment and subsequent analysis was provided by the Office of Naval Research under grants N00014-95-1-0339 and N00014-01-1-0140

    Emerging medical and engineering strategies for the prevention of long-term indwelling catheter blockage

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    Urinary catheters have been used on an intermittent or indwelling basis for centuries, in order to relieve urinary retention and incontinence. Nevertheless, the use of urinary catheters in the clinical setting is fraught with complication, the most common of which is the development of nosocomial urinary tract infections, known as catheter-associated urinary tract infections. Infections of this nature are not only significant owing to their high incidence rate and subsequent economic burden but also to the severe medical consecutions that result. A range of techniques have been employed in recent years, utilising various technologies in attempts to counteract the perilous medical cascade following catheter blockage. This review will focus on the current advancement (within the last 10 years) in prevention of encrustation and blockage of long-term indwelling catheters both from engineering and medical perspectives, with particular emphasis on the importance of stimuli-responsive systems.</p

    Control of mRNA decapping by autoinhibition.

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    5' mediated cytoplasmic RNA decay is a conserved cellular process in eukaryotes. While the functions of the structured core domains in this pathway are well-studied, the role of abundant intrinsically disordered regions (IDRs) is lacking. Here we reconstitute the Dcp1:Dcp2 complex containing a portion of the disordered C-terminus and show its activity is autoinhibited by linear interaction motifs. Enhancers of decapping (Edc) 1 and 3 cooperate to activate decapping by different mechanisms: Edc3 alleviates autoinhibition by binding IDRs and destabilizing an inactive form of the enzyme, whereas Edc1 stabilizes the transition state for catalysis. Both activators are required to fully stimulate an autoinhibited Dcp1:Dcp2 as Edc1 alone cannot overcome the decrease in activity attributed to the C-terminal extension. Our data provide a mechanistic framework for combinatorial control of decapping by protein cofactors, a principle that is likely conserved in multiple 5' mRNA decay pathways

    Iron(II) Active Species in Iron–Bisphosphine Catalyzed Kumada and Suzuki–Miyaura Cross-Couplings of Phenyl Nucleophiles and Secondary Alkyl Halides

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    While previous studies have identified FeMes<sub>2</sub>(SciOPP) as the active catalyst species in iron–SciOPP catalyzed Kumada cross-coupling of mesitylmagnesium bromide and primary alkyl halides, the active catalyst species in cross-couplings with phenyl nucleophiles, where low valent iron species might be prevalent due to accessible reductive elimination pathways, remains undefined. In the present study, in situ Mössbauer and magnetic circular dichroism spectroscopic studies combined with inorganic syntheses and reaction studies are employed to evaluate the in situ formed iron species and identify the active catalytic species in iron–SciOPP catalyzed Suzuki–Miyaura and Kumada cross-couplings of phenyl nucleophiles and secondary alkyl halides. While reductive elimination to form Fe­(η<sup>6</sup>-biphenyl)­(SciOPP) occurs upon reaction of FeCl<sub>2</sub>(SciOPP) with phenyl nucleophiles, this iron(0) species is not found to be kinetically competent for catalysis. Importantly, mono- and bis-phenylated iron­(II)–SciOPP species that form prior to reductive elimination are identified, where both species are found to be reactive toward electrophile at catalytically relevant rates. The higher selectivity toward the formation of cross-coupled product observed for the monophenylated species combined with the undertransmetalated nature of the in situ iron species in both Kumada and Suzuki–Miyaura reactions indicates that Fe­(Ph)­X­(SciOPP) (X = Br, Cl) is the predominant reactive species in cross-coupling. Overall, these studies demonstrate that low-valent iron is not required for the generation of highly reactive species for effective aryl-alkyl cross-couplings
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