Hydrodynamic Characterization of Bile Salt Host-Guest Complexes by Pulsed Field Gradient NMR Spectroscopy

The work described herein is aimed at understanding primary and secondary aggregation of bile salt micelles and how micelles can perform chiral recognition of binapthyl analytes. Previous work with cholate and deoxycholate using micellar electrokinetic chromatography (MEKC) and nuclear magnetic resonance (NMR) has provided insightinto cholate and deoxycholate micelle formation, especially with respect to the critical micelle concentration (CMC). Chiral separations of the model analyte, 1,1â??-binaphthyl-2,2â??-diyl hydrogen phosphate (BNDHP), via cholate (C) and deoxycholate (DC) mediated MEKC separataions previously have shown the DC CMC to be 7-10 mM andthe cholate CMC at 14 mM at ph 12. A second model analyte,1,1â??-binaphthol (BN), was also previously investigated to probe micellar structure, but the MEKC data for this analyte implied a higher CMC, which may be interpreted as secondary aggregation. Thiswork extends the investigation of bile salts to include pulsed field gradient spin echo (PFGSE) NMR experiments being used to gain information about the size and degree of polydispersity of cholate and deoxycholate micelles. Concentrations of cholate below 10mM show a large variation in effective radius likely due to the existence of transient preliminary aggregates. The onset of the primary micelle shows a dramatic increase in effective radius of the micelle in cholate and deoxycholate. In the region of expectedsecondary aggregation a gradual increase of effective radius was observed with cholate; deoxycholate showed a persistent aggregate size in the secondary micelle region that is modulated by the presence of an analyte molecule. Effective radii of cholate anddeoxycholate (individually) were compared with and without R- and S-BNDHP in order to observe the effective radius difference of micelles with and without analyte present. The presence of S-BNDHP consistently resulted in a larger effective aggregate radius incholate and deoxycholate, confirming previous data of the S-BNDHP interacting more with the micelle than R-BNDHP. In total, various NMR techniques, like diffusion NMR can be used to gain a greater understanding of the bile salt micellization process and chiral resolution.

The impact of different glacial boundary conditions on atmospheric dynamics and precipitation in the North Atlantic region

Using a highly resolved atmospheric general circulation model, the impact of different glacial boundary conditions on precipitation and atmospheric dynamics in the North Atlantic region is investigated. Six 30-yr time slice experiments of the Last Glacial Maximum at 21 thousand years before the present (ka BP) and of a less pronounced glacial state – the Middle Weichselian (65 ka BP) – are compared to analyse the sensitivity to changes in the ice sheet distribution, in the radiative forcing and in the prescribed time-varying sea surface temperature and sea ice, which are taken from a lower-resolved, but fully coupled atmosphere-ocean general circulation model. The strongest differences are found for simulations with different heights of the Laurentide ice sheet. A high surface elevation of the Laurentide ice sheet leads to a southward displacement of the jet stream and the storm track in the North Atlantic region. These changes in the atmospheric dynamics generate a band of increased precipitation in the mid-latitudes across the Atlantic to southern Europe in winter, while the precipitation pattern in summer is only marginally affected. The impact of the radiative forcing differences between the two glacial periods and of the prescribed time-varying sea surface temperatures and sea ice are of second order importance compared to the one of the Laurentide ice sheet. They affect the atmospheric dynamics and precipitation in a similar but less pronounced manner compared with the topographic changes.

Simulated winter circulation types in the North Atlantic and European region for preindustrial and glacial conditions

[1] Winter circulation types under preindustrial and glacial conditions are investigated and used to quantify their impact on precipitation. The analysis is based on daily mean sea level pressure fields of a highly resolved atmospheric general circulation model and focuses on the North Atlantic and European region. We find that glacial circulation types are dominated by patterns with an east-west pressure gradient, which clearly differs from the predominantly zonal patterns for the recent past. This is also evident in the frequency of occurrence of circulation types when projecting preindustrial circulation types onto the glacial simulations. The elevation of the Laurentide ice sheet is identified as a major cause for these differences. In areas of strong precipitation signals in glacial times, the changes in the frequencies of occurrence of the circulation types explain up to 60% of the total difference between preindustrial and glacial simulations.