Efficient Conversion of Glucose into Fructose via Extraction-Assisted Isomerization Catalyzed by Endogenous Polyamine Spermine in the Aqueous Phase.

ABSTRACT

In the present study, natural polyamine spermine is demonstrated as a potential basic catalyst for glucose-to-fructose isomerization. For instance, spermine achieves a decent fructose yield (30% wt) and selectivity (74%) during the single-step aqueous phase isomerization under the modest operating conditions (100 °C for 15 min). In addition to the expected reaction byproduct monosugar mannose, spermine also assists in the synthesis of rare and important monosugar, that is, psicose up to 4% wt. Psicose is a zero calorie rare sugar, exhibits a low caloric value, and possesses anti-adipogenic property. A comparative study involving other polyamines concluded that the presence of 20 amines tends to exhibit the most significant impact in improving the target product yield by releasing a higher number of OH- ions, which are responsible for isomerization through the formation of an enediol anion. An attempt was made to further improve the fructose yield through the addition of neutral salts, but it promoted a meager achievement. In an alternate study, a selective extraction strategy was followed for the isolation of fructose from the reaction mixture. The employed aryl monoboronic acid remarkably improved the net fructose concentration, that is, fructose productivity up to 75% wt (cumulative) and 70% selectivity within three consecutive extractions and isomerization cycles, which is comparatively three times shorter than that reported in the literature. Notably, spermine itself provided the essential and necessary basic environment for selective fructose extraction and glucose isomerization, ruling out the use of any external reagents and thus establishing itself as a versatile material suitable for a typical isomerization reaction in an upscaled reactor.