Supramolecular fibrous gels with helical pitch tunable by polarity of alcohol solvents.

A sugar-based, low-molecular-weight gelator 16AG, can gelatinize primary alcohols by forming supramolecular fibers. We obtained non-helical, tape-like fibers in methanol and ethanol but helical fibers in alcohols with at least three carbons. The pitch of the helical fibers became shorter with increasing carbon number.

Supramolecular Organogelation Directed by Weak Noncovalent Interactions in Palmitoylated 1,5-Anhydro-d-Glucitol Derivatives.

We synthesized a series of novel alicyclic compounds by modifying 1,5-anhydro-d-glucitol with two to four palmitoyl chains, and we explored their self-assembly and gelation behaviors in paraffin. The obtained organogels were studied by field emission scanning electron microscopy, atomic force microscopy, variable-temperature Fourier transform IR spectroscopy, X-ray diffraction analysis, polarized optical microscopy, and transmission spectroscopy. While all the palmitoylated derivatives spontaneously formed fibrous networks and gelated the paraffin, an acetylated derivative of 1,5-anhydro-d-glucitol did not gelatinize the solvent, thus indicating the importance of aliphatic chains for gelation. Interestingly, α- and ß- d-glucopyranose with five palmitoyl chains neither gelatinized the solvent nor formed fibrous networks, thus suggesting that the absence of C-1 substitution in 1,5-anhydro-d-glucitol is important for gelation. Fourier transform IR spectroscopy suggested that the formation of weak hydrogen bonds between the carbonyl groups and the C-H groups was the driving force for formation of the supramolecular fibers and for gelation of the solvent.

Development of Novel Low-Molecular-Mass Oil-gelling Agents: Synthesis and Physical Properties of 1,5-Anhydro-D-glucitol and 1,5-Anhydro-D-mannitol Protected with Saturated Linear Fatty Acids.

We have developed a novel low-molecular-mass oil-gelling agent that is electrically neutral, has no nitrogen atoms and consists only of cyclic sugar alcohols and saturated linear fatty acids. The cyclic sugar alcohols were 1,5-anhydro-D-glucitol (1,5-AG) and 1,5-anhydro-D-mannitol (1,5-AM) derived from starch via 1,5-anhydro-D-fructose. Various saturated linear fatty acids with 10 to 18 and 22 carbon atoms were introduced into all the hydroxy groups of 1,5-AG. Various saturated linear fatty acids with 13 to 18 and 22 carbon atoms were introduced into all the hydroxy groups of 1,5-AM. Initially, the gelling ability increased as the carbon number increased, but the gelling ability decreased as the carbon number increased beyond 17 carbons. This trend was similar for both 1,5-AG and 1,5-AM. A comparison of 1,5-AG and 1,5-AM derivatives revealed that 1,5-AG derivatives had greater gelling abilities for different kinds of oils at the same fatty acid length. Further, it was confirmed by SEM observations that a three-dimensional fibrous structure was formed, and this network structure formed the gel and held the oil. Here, we report the synthesis and characteristics of a novel low-molecular-weight gelling agent and its gelation mechanism.

Enzymatic Synthesis of 1,5-Anhydro-4-O-ß-D-glucopyranosyl-D-fructose Using Cellobiose Phosphorylase and Its Spontaneous Decomposition via ß-Elimination.

Cellobiose phosphorylase from Cellvibrio gilvus was used to prepare 1,5-anhydro-4-O-ß-D-glucopyranosyl-D-fructose [ßGlc(1→4)AF] from 1,5-anhydro-D-fructose and α-D-glucose 1-phosphate. ßGlc(1→4)AF decomposed into D-glucose and ascopyrone T via ß-elimination. Higher pH and temperature caused faster decomposition. However, decomposition proceeded significantly even under mild conditions. For instance, the half-life of ßGlc(1→4)AF was 17 h at 30 °C and pH 7.0. Because ßGlc(1→4)AF is a mimic of cellulose, in which the C2 hydroxyl group is oxidized, such decomposition may occur in oxidized cellulose in nature. Here we propose a possible oxidizing pathway by which this occurs.