Travelling on the potential energy surfaces of carbohydrates: comparative application of an exhaustive systematic conformational search with an heuristic search.
The calculated ensembles found by a heuristic conformational search algorithm, CICADA, for three small carbohydrates, ethyl beta-lactoside, methyl alpha-D-galactoside, and methyl beta-D-galactoside, are evaluated in terms of their ability to reproduce time-averaged optical rotation and NMR data. A unique dynamic model for methyl beta-D-galactoside has been obtained by fitting experimental NOESY volumes to the theoretical ones elaborated from the CICADA ensemble internuclear distances with the model-free formalism. In the case of ethyl beta-lactoside, the CICADA ensemble is compared to that of an exhaustive systematic grid-search method. The CICADA algorithm proved to be a very efficient method to find most of the important minima on even very complex potential energy surfaces, and the spectral quality of the CICADA ensemble was found to be of equal quality, if not superior, to that of the exhaustive systematic grid-search method. The CICADA algorithm has several advantages over other conformational search algorithms: (1) It has polynomial dependence of dimensions on computer time in contrast to the grid search, which has exponential dependence, (2) the conformations found are free of artificial harmonic constraint potentials, (3) it passes all barriers amongst families of conformations on conformational hypersurface but spends almost all its time in the essential highly populated areas, (4) the inherent properties of the algorithm make rigorous minimization criteria superfluous and provide good convergence behavior, and (5) as an important spin-off, it provides low-energy interconversion pathways that can, amongst others, be used for estimating adiabatic rotational barriers.
Engelsen
S B
SB
Ingénierie Moléculaire, Institut National de la Recherche Agronomique, Nantes, France.
Koca
J
J
Braccini
I
I
Hervé du Penhoat
C
C
Pérez
S
S
D000465:Algorithms; D002236:Carbohydrate Conformation; D002240:Carbohydrate Sequence; D006027:Glycosides / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008756:Methylgalactosides / Q000737:chemistry*; D008969:Molecular Sequence Data; D015394:Molecular Structure
D006027:Glycosides; D008756:Methylgalactosides; C008245:lactosides