File(s) under permanent embargo
V-Amylose at atomic resolution: X-ray structure of a cycloamylose with 26 glucose residues (cyclomaltohexaicosaose)
journal contribution
posted on 2023-05-18, 11:26 authored by Gessler, K, Uson, I, Takaha, T, Krauss, N, Steven SmithSteven Smith, Okada, S, Sheldrick, GM, Saenger, WThe 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.
History
Publication title
Proceedings of the National Academy of Sciences of The United States of AmericaVolume
96Issue
8Pagination
4246-4251ISSN
0027-8424Department/School
School of Natural SciencesPublisher
Natl Acad SciencesPlace of publication
2101 Constitution Ave Nw, Washington, USA, Dc, 20418Rights statement
Copyright 1999 The National Academy of SciencesRepository Status
- Restricted