The crystal structure of α,α-trehalose dihydrate from three independent X-ray determinations

Abstract

The structure of the dihydrate of the nonreducing disaccharide a,a-trehalose (a-D-glucopyranosyl a-D-glucopyranoside) has been determined independently by direct methods in three different laboratories. There are four units C~2H22Ol~.2H20 in an orthorhombic cell (P212a2a) with a= 12"230 (2), Comparison of coordinates suggests that their standard errors may have been underestimated by a factor of ~2. The a,a-trehalose molecule has approximate C2 symmetry, but there are some significant structural differences between the two chemically equivalent halves. The angles at the ring oxygen atoms are 114-0 and 114-2°; the angle at the glycosidic oxygen is 115.8 °. The two rings have Cl conformations; the conformations about the linking C-O bonds are stabilized by the conformational 6anomeric effect' and also by a complex system of hydrogen bonds involving all of the hydroxyl groups, both water molecules, and one ring oxygen. By hydrogen bonding each glucopyranosy] moiety is linked to the other in the same molecule indirectly through two different water molecules. The helical arrangement of hydrogen bonds about the screw axes parallel to e suggests the possibility of observing ferroelectric behavior.

The crystal and molecular structure of 6,6'-dibromo-6,6'-dideoxy-α,α-trehalose hexaacetate chloroform adduct, C24H32Br2O15.CHCl3

“…These two values are in excellent agreement with those found by Cook & Bugg (1973) in trehalose calcium bromide monohydrate [77.0 (5), -164.6 (5)0] * but differ very significantly from the values of 61.7 (2) and -177.0 (2) ° observed by Brown et al (1972) in trehalose dihydrate.…”

“…First of all, the two glycosyl units are in a symmetrical disposition around the glycosidic oxygen. In fact, in a,a-trehalose calcium bromide monohydrate (Cook & Bugg, 1973) the two glycosyl units are crystallographically related by a twofold axis of rotation passing through the central O atom, while the molecule has approximate C 2 (2) symmetry in the case of a,atrehalose dihydrate (Brown et al, 1972). The second interesting feature is the a-linkage which has a strong bearing on its enzymatic behaviour.…”

“…It is also found in algae, lichens and bacteria and it constitutes the blood sugar of many insects [see for example Defaye, Driguez, Henrissat, Gelas & BarGuilloux (1978), and references cited therein]. The molecule of trehalose, which has been extensively studied by X-ray diffraction methods (Brown, Rohrer, Berking, Beevers, Gould & Simpson, 1972;Cook & Bugg, 1973), has two interesting structural features. First of all, the two glycosyl units are in a symmetrical disposition around the glycosidic oxygen.…”

2,2'-Di-O-acetyl-3,6;3',6'-dianhydro-4,4'-dideoxy-α,α-trehalose

“…Bond lengths and angles agree well with those of methyl 3,6-anhydroa-D-hexopyranosides (Lindberg, Lindberg & Svensson, 1973;Campbell & Harding, 1972), and most other pyranose sugars (Berman, Chu & Jeffrey, 1967). The O(1)--C(1) and O(1)---C(1 ') bond lengths show systematic trends similar to those observed in other a-pyranose sugars (Berman, Chu & Jeffrey, 1967) but are shorter than those in a,a-trehalose (Brown, Rohrer, Berking, Beevers, Gould & Simpson, 1972;Taga, Senma & Osaki, 1972;Jeffrey & Nanni, 1985) and its 3,3-dideoxy derivative (Lee & Koh, 1993). The small C(3)--C(4)---C(5) angles [98.6 (6) (unprimed), 97.8 (7) ° (primed)], which are also observed in 3,6-anhydro-a-o-hexopyranoside derivatives (Lindberg, Lindberg & Svensson, 1973;Campbell & Harding, 1972;Isaac & Kennard, 1972), are a consequence of strain introduced by the cisfused five-membered anhydro ring.…”

Inhibition of Alzheimer amyloid β aggregation by polyvalent trehalose

“…These results indicate that the inhibitory effect of the saccharides was amplified by a multivalency-like protein-saccharide interaction. Trehalose is a unique disaccharide with a clam shell structure [21], which induces the water-like hydrogen bonding with lipids [22] and proteins [23] to preserve the biological activities. The hydrogen bonding formation of trehalose with water clusters was also reported [24].…”