DFT studies of the disaccharide, α-maltose: relaxed isopotential maps
- 作者：Udo Schnupf ; J.L. Willett ; Wayne B. Bosma ; Frank A. Momany
- 关键词：Disaccharide ; Maltose ; Density functional ; Basis set ; Conformation ; Isopotential relaxed maps
- 刊名：Carbohydrate Research
- 出版年：2007
- 期刊代码：15_00086215
- 类别：ch
- 出版时间：5 November 2007
- 卷：342
- 期：15
- 页码：2270-2285
- 文件大小：2011 K
摘要
The disaccharide, α-maltose, forms the molecular basis for the analysis of the structure of starch, and determining the conformational energy landscape as the molecule oscillates around the glycosidic bonds is of importance. Thus, it is of interest to determine, using density functionals and a medium size basis set, a relaxed isopotential contour map plotted as a function of the 
H and ψH dihedral angles. The technical aspects include the method of choosing the starting conformations, the choice of scanning step size, the method of constraining the specific dihedral angles, and the fitting of data to obtain well defined contour maps. Maps were calculated at the B3LYP/6-31+G* level of theory in 5° intervals around the (H, ψH) = (0°, 0°) position, out to 
±30° or greater, for gg–gg′–c, gg–gg′–r, gt–gt′–c, gt–gt′–r, tg–tg′–c, and tg–tg′–r conformers, as well as one-split gg(c)–gg′(r) conformer. The results show that the preferred conformation of α-maltose in vacuo depends strongly upon the hydroxyl group orientations (‘c’/‘r’), but the energy landscape moving away from the minimum-energy position is generally shallow and transitions between conformational positions can occur without the addition of significant energy. Mapped deviations of selected parameters such as the dipole moment; the C1–O1–C4′, H1–C1–O1, and H4′–C4′–O1 bond angles; and deviations in hydroxymethyl rotamers, O5–C5–C6–O6, O5′–C5′–C6′–O6′, C5–C6–O6–H, and C5′–C6′–O6′–H′, are presented. These allow visualization of the structural and energetic changes that occur upon rotation about the glycosidic bonds. Interactions across the bridge are visualized by deviations in H(O2)
O3′, H(O3′)O2, and H1H4′ distances and the H(O2)–O2–C2–C1 and H′(O3′)–O3′–C3′–C4′ hydroxyl dihedral angles.
H and ψH dihedral angles. The technical aspects include the method of choosing the starting conformations, the choice of scanning step size, the method of constraining the specific dihedral angles, and the fitting of data to obtain well defined contour maps. Maps were calculated at the B3LYP/6-31+G* level of theory in 5° intervals around the (H, ψH) = (0°, 0°) position, out to ±30° or greater, for gg–gg′–c, gg–gg′–r, gt–gt′–c, gt–gt′–r, tg–tg′–c, and tg–tg′–r conformers, as well as one-split gg(c)–gg′(r) conformer. The results show that the preferred conformation of α-maltose in vacuo depends strongly upon the hydroxyl group orientations (‘c’/‘r’), but the energy landscape moving away from the minimum-energy position is generally shallow and transitions between conformational positions can occur without the addition of significant energy. Mapped deviations of selected parameters such as the dipole moment; the C1–O1–C4′, H1–C1–O1, and H4′–C4′–O1 bond angles; and deviations in hydroxymethyl rotamers, O5–C5–C6–O6, O5′–C5′–C6′–O6′, C5–C6–O6–H, and C5′–C6′–O6′–H′, are presented. These allow visualization of the structural and energetic changes that occur upon rotation about the glycosidic bonds. Interactions across the bridge are visualized by deviations in H(O2)O3′, H(O3′)O2, and H1H4′ distances and the H(O2)–O2–C2–C1 and H′(O3′)–O3′–C3′–C4′ hydroxyl dihedral angles.