Chiral systems coupling

The point is also made [134] that the very high surface areas and the richly interconnected three-dimensional networks of these micron-sized spaces, coupled with periods of desiccation, could together have produced microenvironments rich in cat-alytically produced complex chemicals and possibly membrane-endosed vesides of bacterial size. These processes would provide the proximate concatenation of lipid vesicular precursors with the complex chemicals that would ultimately produce the autocatalytic and self-replicating chiral systems. A 2.5 km2 granite reef is estimated to contain possibly 1018 catalytic microreactors, open by diffusion to the dynamic reservoir of organic molecules. .. but protected from the dispersive effects of flow and convection [134] as well as protected from the high flux of ultraviolet radiation impinging on the early Earth. [123,137]... 

The SA CSPs have been used in a variety of pharmacokinetic and pharmacodynamic studies. Because of the nature of these columns, they are most often used in coupled achiral-chiral systems. Two examples of this approach are the following ... 

It has been long appreciated that a chiral environment may differentiate any physical property of enantiomeric molecules. NMR spectroscopy is a sensitive probe for the occurrence of interactions between chiral molecules [4]. NMR spectra of enantiomers in an achiral medium are identical because enantiotopic groups display the same values of NMR parameters. Enantiodifferentiation of the spectral parameters (chemical shifts, spin-spin coupling constants, relaxation rates) requires the use of a chiral medium, such as CyDs, that converts the mixture of enantiomers into a mixture of diastereomeric complexes. Other types of chiral systems used in NMR spectroscopy include chiral lanthanide chemical shift reagents [61, 62] and chiral liquid crystals [63, 64). These approaches can be combined. For example, CyD as a chiral solvating medium was used for chiral recognition in the analysis of residual quadrupolar splittings in an achiral lyotropic liquid crystal [65]. 

Abstract The modified equation-of-motion coupled cluster approach of Sekino and Bartlett is extended to computations of the mixed electric-dipole/magnetic-dipole polarizability tensor associated with optical rotation in chiral systems. The approach - referred to here as a linearized equation-of-motion coupled cluster (EOM-CCl) method - is a compromise between the standard EOM method and its linear response counterpart, which avoids the evaluation of computationally expensive terms that are quadratic in the field-perturbed wave functions, but still yields properties that are size-extensive/intensive. Benchmark computations on five representative chiral molecules, including (P)-hydrogen peroxide, (5)-methyloxirane, (5 )-2-chloropropioniuile, (/ )-epichlorohydrin, and (75,45)-norbornenone, demonstrate typically small deviations between the EOM-CCl results and those from coupled cluster linear response theory, and no variation in the signs of the predicted rotations. In addition, the EOM-CCl approach is found to reduce the overall computing time for multi-wavelength-specific rotation computations by up to 34%. 

Enantiopure thiahelicenes can transfer their molecular chirahty to the whole phase of an achiral liquid crystal phase thus acting as dopant systems. Coupling the analysis of CD spectra with the study of cholesteric meso-phases induced in nematic liquid crystals (LC), a model has been proposed for the transfer of chirality from thiahehcene (Al)-114 (Figure 13) to the whole liquid crystal phase (cholesteric induction) (1996JO2013). The dopant thiahehcene presents a twisted chiral surface, which is homochiral with the induced cholesterics as a consequence of the interaction of its... 

Figure 11.3 Typical configuration for the on-line coupling of an achiral and chiral cliro-matograpliic system by means of a switching valve. The non-enantio-resolved solute is isolated on the achiral phase and then stereochemically separated on the chiral phase. Reprinted from G. Subramanian, A Practical Approach to Chiral Separation by Liquid Chromatography, 1994, pp. 357-396, with permission from Wiley-VCH.

The type of CSPs used have to fulfil the same requirements (resistance, loadabil-ity) as do classical chiral HPLC separations at preparative level [99], although different particle size silica supports are sometimes needed [10]. Again, to date the polysaccharide-derived CSPs have been the most studied in SMB systems, and a large number of racemic compounds have been successfully resolved in this way [95-98, 100-108]. Nevertheless, some applications can also be found with CSPs derived from polyacrylamides [11], Pirkle-type chiral selectors [10] and cyclodextrin derivatives [109]. A system to evaporate the collected fractions and to recover and recycle solvent is sometimes coupled to the SMB. In this context the application of the technique to gas can be advantageous in some cases because this part of the process can be omitted [109]. 

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