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V-Amylose at atomic resolution: X-ray structure of a cycloamylose with 26 glucose residues (cyclomaltohexaicosaose)

Citation

Gessler, K and Uson, I and Takaha, T and Krauss, N and Smith, SM and Okada, S and Sheldrick, GM and Saenger, W, V-Amylose at atomic resolution: X-ray structure of a cycloamylose with 26 glucose residues (cyclomaltohexaicosaose), Proceedings of the National Academy of Sciences of The United States of America, 96, (8) pp. 4246-4251. ISSN 0027-8424 (1999) [Refereed Article]

Copyright Statement

Copyright 1999 The National Academy of Sciences

DOI: doi:10.1073/pnas.96.8.4246

Abstract

The amylose fraction of starch occurs in double-helical A- and B-amyloses and the single-helical V-amylose. The latter contains a channel-like central cavity that is able to include molecules, "iodine’s blue" being the best-known representative. Molecular models of these amylose forms have been deduced by solid state 13C cross-polarization/magic angle spinning NMR and by x-ray fiber and electron diffraction combined with computer-aided modeling. They remain uncertain, however, as no structure at atomic resolution is available. We report here the crystal structure of a hydrated cycloamylose containing 26 glucose residues (cyclomaltohexaicosaose, CA26), which has been determined by real/reciprocal space recycling starting from randomly positioned atoms or from an oriented diglucose fragment. This structure provides conclusive evidence for the structure of V-amylose, as the macrocycle of CA26 is folded into two short left-handed V-amylose helices in antiparallel arrangement and related by twofold rotational pseudosymmetry. In the V-helices, all glucose residues are in syn orientation, forming systematic interglucose O(3)n⋅⋅⋅O(2)n+l and O(6)n⋅⋅⋅O(2)n+6/O(3)n+6 hydrogen bonds; the central cavities of the V-helices are filled by disordered water molecules. The folding of the CA26 macrocycle is characterized by typical "band-flips" in which diametrically opposed glucose residues are in anti rather than in the common syn orientation, this conformation being stabilized by interglucose three-center hydrogen bonds with O(3)n as donor and O(5)n+l, O(6)n+l as acceptors. The structure of CA26 permitted construction of an idealized V-amylose helix, and the band-flip motif explains why V-amylose crystallizes readily and may be packed tightly in seeds.

Item Details

Item Type:Refereed Article
Keywords:v-amylose, cyclomaltohexaicosaose, starch, x-ray structure
Research Division:Biological Sciences
Research Group:Plant Biology
Research Field:Plant Physiology
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Biological Sciences
Author:Smith, SM (Professor Steven Smith)
ID Code:101563
Year Published:1999
Web of Science® Times Cited:145
Deposited By:Plant Science
Deposited On:2015-06-25
Last Modified:2015-09-21
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