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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 9 (1986), S. 308-309 
    ISSN: 0935-6304
    Keywords: High performance liquid chromatography, HPLC ; Reverse phase ; Internal standard ; Trimellitic anhydride ; Air sample ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0170-2041
    Keywords: Resolution, kinetic ; Chiral tertiary amines ; Chiral esters ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Kinetic Resolutions Starting with rac-Alcohols or rac-Acyl Halides Using Optically Active Inductor BasesIn the reaction of one mole equivalent of achiral acyl halides with two equivalents of rac-alcohols in the presence of one equivalent of an optically active inductor base (tertiary amine) partially optically active esters and partially optically active alcohols are formed, having in some cases high optical purity (60 - 70%). The alcohol moiety of the ester and the unchanged alcohol are of opposite configuration. Treatment of two equivalents of rac-acylhalides with one equivalent of an achiral alcohol and an inductor base also leads to a high degree of optical induction. The carbonic acid moiety in the ester and the unchanged acid are of opposite configuration. The optical induction is influenced a) by the ligands linked to the reaction centers, b) by the relative quantities of the reacting partners, c) by the solvent, and d) by the temperature.
    Notes: Bei der Umsetzung eines Moläquivalents achiraler Carbonsäurehalogenide mit zwei Moläquivalenten rac-Alkoholen entstehen unter Mitwirkung von einem Moläquivalent einer optisch aktiven Induktorbase (tertiäres Amin) partiell optisch aktive Ester sowie partiell optisch aktive Alkohole in zum Teil hoher optischer Reinheit (60 - 70%). Der im Ester gebundene Anteil an Alkohol sowie der nicht umgesetzte Alkohol haben entgegengesetzte Konfiguration. Der Induktionsgrad ist ähnlich hoch, wenn man zwei Moläquivalente eines rac-Carbonsäurehalogenids mit je einem Moläquivalent eines achiralen Alkohols und einer Induktorbase umsetzt. Der Carbonsäureanteil im Ester und die freie Säure haben entgegengesetzte Konfiguration. Die optischen Induktionen werden beeinflußt a) durch die Art der mit den Reaktionszentren verknüpften Liganden, b) durch die relativen Mengen der Reaktionspartner, c) durch das Lösungsmittel und d) durch die Temperatur.
    Additional Material: 8 Tab.
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  • 3
    ISSN: 0377-0486
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Raman (3500-20 cm-1) and infrared (3500-50 cm-1) spectra of gaseous and solid methylcyclobutane and methyl-d3-cyclobutane have been recorded. Additionally, the Raman spectra of the pure liquids have been recorded and qualitative depolarization values have been obtained. The spectra have been interpreted on the basis that both the axial and equatorial conformers are present in the fluid phases and that the equatorial form is thermodynamically preferred and the only form present in the annealed solid. All 39 of the normal vibrational modes have been assigned for both the d0 and d3 compounds. An abundance of spectral evidence is presented which indicates extensive coupling between the vibrations associated with the ring and those of the methyl group. The CH3 internal torsional mode has been observed in the Raman spectrum of the solid at 232 cm-1 and utilizing this frequency the periodic threefold barrier to internal rotation has been calculated to be 1190 cm-1 (3.40 kcal mol-1). The fundamental ring puckering mode has been assigned from the Raman spectra of the gases to weak features observed at 161 and 154 cm-1 for the d0 and d3 compounds, respectively. All of these results are compared with the corresponding quantities for some similar molecules.
    Additional Material: 4 Ill.
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  • 4
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2009. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 39 (2009): 107-124, doi:10.1175/2008JPO3952.1.
    Description: In most estuarine systems it is assumed that the dominant along-channel momentum balance is between the integrated pressure gradient and bed stress. Scaling the amplitude of the estuarine circulation based on this balance has been shown to have predictive skill. However, a number of authors recently highlighted important nonlinear processes that contribute to the subtidal dynamics at leading order. In this study, a previously validated numerical model of the Hudson River estuary is used to examine the forces driving the residual estuarine circulation and to test the predictive skill of two linear scaling relationships. Results demonstrate that the nonlinear advective acceleration terms contribute to the subtidal along-channel momentum balance at leading order. The contribution of these nonlinear terms is driven largely by secondary lateral flows. Under a range of forcing conditions in the model runs, the advective acceleration terms nearly always act in concert with the baroclinic pressure gradient, reinforcing the residual circulation. Despite the strong contribution of the nonlinear advective terms to the subtidal dynamical balance, a linear scaling accurately predicts the strength of the observed residual circulation in the model. However, this result is largely fortuitous, as this scaling does not account for two processes that are fundamental to the estuarine circulation. The skill of this scaling results because of the compensatory relationship between the contribution of the advective acceleration terms and the suppression of turbulence due to density stratification. Both of these processes, neither of which is accounted for in the linear scaling, increase the residual estuarine circulation but have an opposite dependence on tidal amplitude and, consequently, strength of stratification.
    Description: This research was supported by the Beacon Institute for Rivers and Estuaries—Woods Hole Oceanographic Institution postdoctoral fellowship program, as well as NSF Grants OCE-0452054 and OCE-0451740.
    Keywords: Advection ; Estuarine circulation ; Friction ; Density currents ; Baroclinic flows
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 5
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2007. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 37 (2007): 1859-1877, doi:10.1175/jpo3088.1.
    Description: A series of dye releases in the Hudson River estuary elucidated diapycnal mixing rates and temporal variability over tidal and fortnightly time scales. Dye was injected in the bottom boundary layer for each of four releases during different phases of the tide and of the spring–neap cycle. Diapycnal mixing occurs primarily through entrainment that is driven by shear production in the bottom boundary layer. On flood the dye extended vertically through the bottom mixed layer, and its concentration decreased abruptly near the base of the pycnocline, usually at a height corresponding to a velocity maximum. Boundary layer growth is consistent with a one-dimensional, stress-driven entrainment model. A model was developed for the vertical structure of the vertical eddy viscosity in the flood tide boundary layer that is proportional to u2*/N∞, where u* and N∞ are the bottom friction velocity and buoyancy frequency above the boundary layer. The model also predicts that the buoyancy flux averaged over the bottom boundary layer is equal to 0.06N∞u2* or, based on the structure of the boundary layer equal to 0.1NBLu2*, where NBL is the buoyancy frequency across the flood-tide boundary layer. Estimates of shear production and buoyancy flux indicate that the flux Richardson number in the flood-tide boundary layer is 0.1–0.18, consistent with the model indicating that the flux Richardson number is between 0.1 and 0.14. During ebb, the boundary layer was more stratified, and its vertical extent was not as sharply delineated as in the flood. During neap tide the rate of mixing during ebb was significantly weaker than on flood, owing to reduced bottom stress and stabilization by stratification. As tidal amplitude increased ebb mixing increased and more closely resembled the boundary layer entrainment process observed during the flood. Tidal straining modestly increased the entrainment rate during the flood, and it restratified the boundary layer and inhibited mixing during the ebb.
    Description: The work was supported by the National Science Foundation Grant OCE00-95972 (W. Geyer, J. Lerczak), OCE00-99310 (R. Houghton), and OCE00-95913 (R. Chant, E. Hunter).
    Keywords: Estuaries ; Boundary layer ; Mixing ; Tides ; Friction
    Repository Name: Woods Hole Open Access Server
    Type: Article
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