Conformations of some lower-size large-ring cyclodextrins derived from conformational search with molecular dynamics and principal component analysis

Computational studies were conducted on the conformations of some lower-size large-ring cyclodextrins, CDn (n = 11, 12, 13, 15, 16, 17). Principal component analysis (PCA) was applied for post-processing of trajectories from conformational search based on 100.0 ns molecular dynamics (MD) simulations. The dominant PCA modes for concerted motions of the macroring atoms were monitored in a lower-dimensions subspace. The first six lowest indexed principal components contribute more than 90% of the total atomic motions in all cases, with about 70% (CD12) to 90% (CD17) contribution coming from the three highest-eigenvalue principal components. Representative average geometries of the cyclodextrin macrorings were also obtained for the whole simulation and for the ten 10.0 ns time intervals of the simulation. We concluded that the whole set of structures could be sorted into two clearly distinguished groups, separated by the figure-eight conformation of CD14: (i) open bent boat-like macrorings (CD11 to CD13), and (ii) two winded single helical strands (an anti-parallel double helix with foldbacks at each end), CD15 to CD17, shaped as number eight for the odd-number-residues cases, CD15 and CD17. CD13 and CD14 mark the borderline between lower and higher flexibilities of the lower-size LR-CDs macrorings.

► Computational studies were conducted on the conformations of some lower-size large-ring cyclodextrins, CDn (n = 11,12,13,15,16,17). ► The whole set of structures could be sorted into two clearly distinguished groups. ► CD11 to CD13 present open bent boat-like macrorings. ► CD15 to CD17 display two winded single helical strands. ► CD13 and CD14 mark the borderline between lower and higher flexibilities of the macrorins.