A simple analysis of the influence of the solvent-induced electronic polarization on the N-15 magnetic shielding of pyridine in water

Electronic polarization induced by the interaction of a reference molecule with a liquid environment is expected to affect the magnetic shielding constants. Understanding this effect using realistic theoretical models is important for proper use of nuclear magnetic resonance in molecular characterization. In this work, we consider the pyridine molecule in water as a model system to briefly investigate this aspect. Thus, Monte Carlo simulations and quantum mechanics calculations based on the B3LYP/6-311++G (d,p) are used to analyze different aspects of the solvent effects on the N-15 magnetic shielding constant of pyridine in water. This includes in special the geometry relaxation and the electronic polarization of the solute by the solvent. The polarization effect is found to be very important, but, as expected for pyridine, the geometry relaxation contribution is essentially negligible. Using an average electrostatic model of the solvent, the magnetic shielding constant is calculated as -58.7 ppm, in good agreement with the experimental value of -56.3 ppm. The explicit inclusion of hydrogen-bonded water molecules embedded in the electrostatic field of the remaining solvent molecules gives the value of -61.8 ppm.

Tracing latitudinal gradient, river discharge and water masses along the subtropical South American coast using benthic Foraminifera assemblages

More than 30% of Buccella peruviana (D'Orbigny), Globocassidulina crassa porrecta (Earland & Heron-Allen), Cibicides mackannai (Galloway & Wissler) and C. refulgens (Montfort) indicate the presence of cold Sub Antarctic Shelf Water in winter, from 33.5 to 38.3º S, deeper than 100 m, in the southern part of the study area. In summer, the abundance of this association decreases to less than 15% around 37.5-38.9º S where two species (Globocassidulina subglobosa (Brady), Uvigerina peregrina (Cushman) take over. G. subglobosa, U. peregrina, and Hanzawaia boueana (D'Orbigny) are found at 27-33º S in both seasons in less than 55 m deep in the northern part, and are linked with warm Subtropical Shelf Water and Tropical Water. Freshwater influence was signalized by high silicate concentration and by the presence of Pseudononion atlanticum (Cushman), Bolivina striatula (Cushman), Buliminella elegantissima (D'Orbigny), Bulimina elongata (D'Orbigny), Elphidium excavatum (Terquem), E. poeyanum (D'Orbigny), Ammobaculites exiguus (Cushman & Brönnimann), Arenoparrella mexicana (Kornfeld), Gaudryina exillis (Cushman & Brönnimann), Textularia earlandi (Parker) and thecamoebians in four sectors of the shelf. The presence of Bulimina marginata (D'Orbigny) between 34.1-32.8º S in the winter and 34.2-32.7º S in the summer indicates that the influence of the Subtropical Shelf Front on the sediment does not change seasonally, otherwise, the presence of Angulogerina angulosa (Williamson) in the winter, only in Mar del Plata (38.9º S), show that Malvinas currents are not influencing the sediment in the summer.