Hustede, H; Haberstroh, HJ; Schinzig, E
d‐Gluconic acid [526‐95‐4], 1,2,3,4,5‐pentahydroxy pentane‐1‐carboxylic acid, C6H12O7, Mr 196.16, was discovered in 1870 by Hlasiwetz and Habermann during the oxidation of glucose with chlorine. The substance was isolated in the form of its barium and calcium salts. Several authors subsequently reported that gluconic acid could be obtained by treatment of various mono‐, di‐, and polysaccharides with oxidizing agents such as elemental halogen, copper(II) or hexacyanoferrate(III) salts, or mercury(II) oxide. Depending on the type of sugar and the oxidant employed, byproducts of the reaction include formic acid, glycolic acid, oxalic acid, and carbon dioxide.
As early as 1880 Boutroux recognized that gluconic acid was produced, together with acetic acid, by the oxidative action of Acetobacter aceti on glucose. This characteristic was also found to be associated with numerous other bacteria 1. Molliard was the first to report the presence of gluconic acid in cultures of Sterigmatocystis nigra, now known as Aspergillus niger 2. The currently preferred method for preparing gluconic acid and its derivatives with the aid of Aspergillus strains is based on the work of a number of authors 3. The catalytic activity of the enzyme glucose oxidase was first described by Müller 4.
During the 1930s anodic oxidation was suggested for the preparation of calcium gluconate 5; proposals for catalytic oxidation of glucose with the aid of air or oxygen followed somewhat later 6.