Graduate Thesis Or Dissertation
 

Circular dichroism of amylose and glucose oligosaccharides in the vacuum ultraviolet

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  • The circular dichroism spectra of amylose, the maltose oligomers, cellobiose, and the cycloamyloses are measured in aqueous solution to 1640 A. Two bands are found in this region. The long wavelength band is assigned to the ether chromophores; the short wavelength band is assigned to the hydroxyls and further ether transitions. An examination of chromophorically equivalent but conformationally different glucans demonstrates that the circular dichroism of glucans is sensitive to conformation. However, the conformation of the subunits in the maltose oligomer series is independent of chainlength. The conformation of the interior maltosyl groups of this series are all approximately equivalent, and the conformation of the end groups are the same for each oligomer and only one glucosyl subunit in length. A comparison of the amylose and cycloamylose spectra indicates that amylose is substantially biased in its chirality. Since there is no chain length dependence, the oligomers must have the same chirality bias. The data of this study is consistent with conformational calculations on amylose which predict that the maltosyl subunits of amylose are restricted to a small region on its conformational map which includes the V form helix. The butanol complex of amylose, which is believed to have a V form helical conformation, has a circular dichroism similar to free aqueous amylose, indicating that maltosyl subunits of amylose are approximately equivalent for these two species. However, since heated amylose is precluded from having a helical conformation, the temperature insensitivity of the free amylose spectra shows that the maltosyl subunits of amylose are not identically V form. This is consistent with a model for amylose which forms a loose extended helix.
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