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  • 1
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 27 (1989), S. 887-891 
    ISSN: 0749-1581
    Keywords: EPR ; ENDOR ; Chiral nitroxides ; Restricted rotation ; Chiral recognition ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Racemic and achiral alkyl aryl nitroxides were examined at various temperatures. The restricted rotation of the aminoxyl substituents was indicated both by the β-proton coupling constants and by the inequivalence of the aromatic ortho protons. These results are interpreted by the presence of two different rotamers which may lead to two splitting constants for the β-proton. The capability for inter- and intra-molecular hydrogen bond formation in the nitroxides investigated was demonstrated. However, complexes consisting of chiral radicals and chiral auxiliaries do not show hyperfine structures which unambiguously indicate diastereomeric species. Therefore, hydrogen bonding between chiral molecules is not sufficient for chiral recognition if an alteration of the hyperconjugation angle does not occur. Simple steric interactions can result in the doubling of the β-proton coupling constant, independently of diastereomeric complex formation.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2012. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Geochemical Cycles 26 (2012): GB2035, doi:10.1029/2011GB004141.
    Description: The fractionation of silicon (Si) stable isotopes by biological activity in the surface ocean makes the stable isotope composition of silicon (δ30Si) dissolved in seawater a sensitive tracer of the oceanic biogeochemical Si cycle. We present a high-precision dataset that characterizes the δ30Si distribution in the deep Atlantic Ocean from Denmark Strait to Drake Passage, documenting strong meridional and smaller, but resolvable, vertical δ30Si gradients. We show that these gradients are related to the two sources of deep and bottom waters in the Atlantic Ocean: waters of North Atlantic and Nordic origin carry a high δ30Si signature of ≥+1.7‰ into the deep Atlantic, while Antarctic Bottom Water transports Si with a low δ30Si value of around +1.2‰. The deep Atlantic δ30Si distribution is thus governed by the quasi-conservative mixing of Si from these two isotopically distinct sources. This disparity in Si isotope composition between the North Atlantic and Southern Ocean is in marked contrast to the homogeneity of the stable nitrogen isotope composition of deep ocean nitrate (δ15N-NO3). We infer that the meridional δ30Si gradient derives from the transport of the high δ30Si signature of Southern Ocean intermediate/mode waters into the North Atlantic by the upper return path of the meridional overturning circulation (MOC). The basin-scale deep Atlantic δ30Si gradient thus owes its existence to the interaction of the physical circulation with biological nutrient uptake at high southern latitudes, which fractionates Si isotopes between the abyssal and intermediate/mode waters formed in the Southern Ocean.
    Description: This work was supported by Swiss National Science Foundation grants 200021-116473 and 200020-130361.
    Description: 2012-12-19
    Keywords: Atlantic Ocean ; Southern Ocean ; Silicon isotopes
    Repository Name: Woods Hole Open Access Server
    Type: Article
    Format: text/plain
    Format: application/vnd.ms-excel
    Format: application/pdf
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