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  • 1
    ISSN: 0941-1216
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular Geometry and Excited Electronic States. XXIV. Theoretical Contribution to the S0 and S1 Molecular Structure and to the Sp ← S0 Electronic Spectral Behaviour of 1,4-Distyryl Benzene an of its Doubly-Charged IonsFor selected configurations of 1,4-distyryl benzene and its doubly-charged ions the completely-optimized molecular geometries of the S0 and S1 states are presented. The structural peculiarities and differences are discussed. The Sp ← S0 electronic spectral data calculated on this basis are given and compared with available experimental results.
    Additional Material: 3 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 30 (1965), S. 256-261 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bei der thermischen oder photolytischen Zersetzung von Di-tert.-butylperoxid in Methanol, Äthanol, n-Propanol, Isopropanol und Benzylalkohol werden Äthylenglykol, 2,3-Butylenglykol, 3,4-Hexylenglykol, Pinakol und Hydrobenzoin mit Ausbeuten von 15 bis 70% gebildet. Bei der thermischen Zersetzung von Di-tert.-butylperoxid in einem Methanol-Äthanol-Gemisch bzw. Methanol-Äthylenglykol-Gemisch entstehen 1,2-Propylenglykol neben Äthylenglykol und 2,3-Butylenglykol bzw. Glycerin neben Äthylenglykol und Erythrit.
    Additional Material: 1 Tab.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 28 (1945), S. 1677-1684 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 28 (1945), S. 576-582 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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  • 5
    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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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 393 (1912), S. 29-60 
    ISSN: 0075-4617
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 613 (1958), S. 137-144 
    ISSN: 0075-4617
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Zur Bestimmung der Reduzierbarkeit von Tetrazoliumsalzen werden diese mit halbreduzierten Redoxfarbstoffen in modifizierten THUNBERG-Gefäßen zusammengebracht. Das Eintreten oder Ausbleiben der Färbung zeigt an, zwischen welchen Redox-Potentialwerten das Tetrazoliumsalz einzuordnen ist. Auf Grund der Eigenschaft der Tetrazoliumsalze, in ihrer Reduzierbarkeit weitgehend pH-unabhängig zu sein, während das Potential des Bezugssystems pH-abhängig ist, bieten sich mit einem Redox-Farbstoff zahlreiche zur nahen Potentialeingrenzung geeignete Bezugs-Redoxpotentiale. Je nach Tetrazoliumsalz wurden Potentiale der Reduzierbarkeit zwischen  -  290 und + 110mV gemessen.
    Additional Material: 1 Ill.
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  • 8
    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): 915-933, doi:10.1175/2008JPO3933.1.
    Description: The temporal response of the length of a partially mixed estuary to changes in freshwater discharge Qf and tidal amplitude UT is studied using a 108-day time series collected along the length of the Hudson River estuary in the spring and summer of 2004 and a long-term (13.4 yr) record of Qf, UT, and near-surface salinity. When Qf was moderately high, the tidally averaged length of the estuary L5, here defined as the distance from the mouth to the up-estuary location where the vertically averaged salinity is 5 psu, fluctuated by more than 47 km over the spring–neap cycle, ranging from 28 to 〉75 km. During low flow periods, L5 varied very little over the spring–neap cycle and approached a steady length. The response is quantified and compared to predictions of a linearized model derived from the global estuarine salt balance. The model is forced by fluctuations in Qf and UT relative to average discharge Qo and tidal amplitude UTo and predicts the linear response time scale τ and the steady-state length Lo for average forcing. Two vertical mixing schemes are considered, in which 1) mixing is proportional to UT and 2) dependence of mixing on stratification is also parameterized. Based on least squares fits between L5 and estuary length predicted by the model, estimated τ varied by an order of magnitude from a period of high average discharge (Qo = 750 m3 s−1, τ = 4.2 days) to a period of low discharge (Qo = 170 m3 s−1, τ = 40.4 days). Over the range of observed discharge, Lo Qo−0.30±0.03, consistent with the theoretical scaling for an estuary whose landward salt flux is driven by vertical estuarine exchange circulation. Estimated τ was proportional to the discharge advection time scale (LoA/Qo, where A is the cross-sectional area of the estuary). However, τ was 3–4 times larger than the theoretical prediction. The model with stratification-dependent mixing predicted variations in L5 with higher skill than the model with mixing proportional to UT. This model provides insight into the time-dependent response of a partially stratified estuary to changes in forcing and explains the strong dependence of the amplitude of the spring–neap response on freshwater discharge. However, the utility of the linear model is limited because it assumes a uniform channel, and because the underlying dynamics are nonlinear, and the forcing Qf and UT can undergo large amplitude variations. River discharge, in particular, can vary by over an order of magnitude over time scales comparable to or shorter than the response time scale of the estuary.
    Description: This study was generously funded by Hudson River Foundation Grant 005/03A and NSF Grant OCE-0452054. Lerczak also received partial support from the Woods Hole Center for Oceans and Human Health, NSF Grant OCE-0430724 and NIEHS Grant 1-P50-ES012742-01.
    Keywords: Estuaries ; Rivers ; Tides ; Stability ; Vertical motion
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 9
    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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  • 10
    Publication Date: 2022-05-25
    Description: Author Posting. © American Meteorological Society, 2008. 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 38 (2008): 418-434, doi:10.1175/2007JPO3372.1.
    Description: Stratification and turbulent mixing exhibit a flood–ebb tidal asymmetry in estuaries and continental shelf regions affected by horizontal density gradients. The authors use a large-eddy simulation (LES) model to investigate the penetration of a tidally driven bottom boundary layer into stratified water in the presence of a horizontal density gradient. Turbulence in the bottom boundary layer is driven by bottom stress during flood tides, with low-gradient (Ri) and flux (Rf) Richardson numbers, but by localized shear during ebb tides, with Ri = ¼ and Rf = 0.2 in the upper half of the boundary layer. If the water column is unstratified initially, the LES model reproduces periodic stratification associated with tidal straining. The model results show that the energetics criterion based on the competition between tidal straining and tidal stirring provides a good prediction for the onset of periodic stratification, but the tidally averaged horizontal Richardson number Rix has a threshold value of about 0.2, which is lower than the 3 suggested in a recent study. Although the tidal straining leads to negative buoyancy flux on flood tides, the authors find that for typical values of the horizontal density gradient and tidal currents in estuaries and shelf regions, buoyancy production is much smaller than shear production in generating turbulent kinetic energy.
    Description: This work is supported by Grants OCE-0451699 and OCE-0451740 from the National Science Foundation.
    Keywords: Tides ; Mixing ; Large eddy simulations
    Repository Name: Woods Hole Open Access Server
    Type: Article
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