1911 Encyclopædia Britannica/Glucose

GLUCOSE (from Gr. γλυκύς, sweet), a carbohydrate of the formula C₆H₁₂O₆; it may be regarded as the aldehyde of sorbite. The name is applied in commerce to a complex mixture of carbohydrates obtained by boiling starch with dilute mineral acids; in chemistry, it denotes, with the prefixes d, l and d + l (or i), the dextro-rotatory, laevo-rotatory and inactive forms of the definite chemical compound defined above. The d modification is of the commonest occurrence, the other forms being only known as synthetic products; for this reason it is usually termed glucose, simply; alternative names are dextrose, grape sugar and diabetic sugar, in allusion to its right-handed optical rotation, its occurrence in large quantity in grapes, and in the urine of diabetic patients respectively. In the vegetable kingdom glucose occurs, always in admixture with fructose, in many fruits, especially grapes, cherries, bananas, &c.; and in combination, generally with phenols and aldehydes belonging to the aromatic series, it forms an extensive class of compounds termed glucosides. It appears to be synthesized in the plant tissues from carbon dioxide and water, formaldehyde being an intermediate product; or it may be a hydrolytic product of a glucoside or of a polysaccharose, such as cane sugar, starch, cellulose, &c. In the plant it is freely converted into more complex sugars, poly-saccharoses and also proteids. In the animal kingdom, also, it is very widely distributed, being sometimes a normal and sometimes a pathological constituent of the fluids and tissues; in particular, it is present in large amount in the urine of those suffering from diabetes, and may be present in nearly all the body fluids. It also occurs in honey, the white appearance of candied honey being due to its separation.

Pure d-glucose, which may be obtained synthetically (see Sugar) or by adding crystallized cane sugar to a mixture of 80% alcohol and 1/15 volume of fuming hydrochloric acid so long as it dissolves on shaking, crystallizes from water or alcohol at ordinary temperatures in nodular masses, composed of minute six-sided plates, and containing one molecule of water of crystallization. This product melts at 86° C., and becomes anhydrous when heated to 110° C. The anhydrous compound can also be prepared, as hard crusts melting at 146°, by crystallizing concentrated aqueous solutions at 30° to 35°. It is very soluble in water, but only slightly soluble in strong alcohol. Its taste is somewhat sweet, its sweetening power being estimated at from 1/2 to 3/5 that of cane sugar. When heated to above 200° it turns brown and produces caramel, a substance possessing a bitter taste, and used, in its aqueous solution or otherwise, under various trade names, for colouring confectionery, spirits, &c. The specific rotation of the plane of polarized light by glucose solutions is characteristic. The specific rotation of a freshly prepared solution is 105°, but this value gradually diminishes to 52.5°, 24 hours sufficing for the transition in the cold, and a few minutes when the solution is boiled. This phenomenon has been called mutarotation by T. M. Lowry. The specific rotation also varies with the concentration; this is due to the dissociation of complex molecules into simpler ones, a view confirmed by cryoscopic measurements.

Glucose may be estimated by means of the polarimeter, i.e. by determining the rotation of the plane of polarization of a solution, or, chemically, by taking advantage of its property of reducing alkaline copper solutions. If a glucose solution be added to copper sulphate and much alkali added, a yellowish-red precipitate of cuprous hydrate separates, slowly in the cold, but immediately when the liquid is heated; this precipitate rapidly turns red owing to the formation of cuprous oxide. In 1846 L. C. A. Barreswil found that a strongly alkaline solution of copper sulphate and potassium sodium tartrate (Rochelle salt) remained unchanged on boiling, but yielded an immediate precipitate of red cuprous oxide when a solution of glucose was added. He suggested that the method was applicable for quantitatively estimating glucose, but its acceptance only followed after H. von Fehling’s investigation. “Fehling’s solution” is prepared by dissolving separately 34.639 grammes of copper sulphate, 173 grammes of Rochelle salt, and 71 grammes of caustic soda in water, mixing and making up to 1000 ccs.; 10 ccs. of this solution is completely reduced by 0.05 grammes of hexose. Volumetric methods are used, but the uncertainty of the end of the reaction has led to the suggestion of special indicators, or of determining the amount of cuprous oxide gravimetrically.

Chemistry.—In its chemical properties glucose is a typical oxyaldehyde or aldose. The aldehyde group reacts with hydrocyanic acid to produce two stereo-isomeric cyanhydrins; this isomerism is due to the conversion of an originally non-asymmetric carbon atom into an asymmetric one. The cyanhydrin is hydrolysable to an acid, the lactone of which may be reduced by sodium amalgam to a glucoheptose, a non-fermentable sugar containing seven carbon atoms. By repeating the process a non-fermentable gluco-octose and a fermentable glucononose may be prepared. The aldehyde group also reacts with phenyl hydrazine to form two phenylhydrazones; under certain conditions a hydroxyl group adjacent to the aldehyde group is oxidized and glucosazone is produced; this glucosazone is decomposed by hydrochloric acid into phenyl hydrazine and the keto-aldehyde glucosone. These transformations are fully discussed in the article Sugar. On reduction glucose appears to yield the hexahydric alcohol d-sorbite, and on oxidation d-gluconic and d-saccharic acids. Alkalis partially convert it into d-mannose and d-fructose. Baryta and lime yield saccharates, e.g. C₆H₁₂O₆·BaO, precipitable by alcohol.

	CH2OH		CH2OH
	ĊH·OH		ĊH·OH
O	ĊH	O	ĊH
	(ĊH·OH)2		(ĊH·OH)2
HĊ·OH		HO·ĊH
α-glucose			β-glucose

The constitution of glucose was established by H. Kiliani in 1885–1887, who showed it to be CH₂OH·(CH·OH)₄·CHO. The subject was taken up by Emil Fischer, who succeeded in synthesizing glucose, and also several of its stereo-isomers, there being 16 according to the Le Bel-van’t Hoff theory (see Stereo-Isomerism and Sugar). This open chain structure is challenged in the views put forward by T. M. Lowry and E. F. Armstrong. In 1895 C. Tanret showed that glucose existed in more than one form, and he isolated α, β and γ varieties with specific rotations of 105°, 52.5° and 22°. It is now agreed that the β variety is a mixture of the α and γ. This discovery explained the mutarotation of glucose. In a fresh solution α-glucose only exists, but on standing it is slowly transformed into γ-glucose, equilibrium being reached when the α and γ forms are present in the ratio 0.368 : 0.632 (Tanret, Zeit. physikal. Chem., 1905, 53, p. 692). It is convenient to refer to these two forms as α and β. Lowry and Armstrong represent these compounds by the following spatial formulae which postulate a γ-oxidic structure, and 5 asymmetric carbon atoms, i.e. one more than in the Fischer formulae. These formulae are supported by many considerations, especially by the selective action of enzymes, which follows similar lines with the α- and β-glucosides, i.e. the compounds formed by the interaction of glucose with substances generally containing hydroxyl groups (see Glucoside).

Fermentation of Glucose.—Glucose is readily fermentable. Of the greatest importance is the alcoholic fermentation brought about by yeast cells (Saccharomyces cerevisiae seu vini); this follows the equation C₆H₁₂O₆ = 2C₂H₆O + 2CO₂, Pasteur considering 94 to 95% of the sugar to be so changed. This character is the base of the plan of adding glucose to wine and beer wort before fermenting, the alcohol content of the liquid after fermentation being increased. Some fusel oil, glycerin and succinic acid appear to be formed simultaneously, but in small amount. Glucose also undergoes fermentation into lactic acid (q.v.) in the presence of the lactic acid bacillus, and into butyric acid if the action of the preceding ferment be continued, or by other bacilli. It also yields, by the so-called mucous fermentation, a mucous, gummy mass, mixed with mannitol and lactic acid.

We may here notice the frequent production of glucose by the action of enzymes upon other carbohydrates. Of especial note is the transformation of maltose by maltase into glucose, and of cane sugar by invertase into a mixture of glucose and fructose (invert sugar); other instances are: lactose by lactase into galactose and glucose; trehalose by trehalase into glucose; melibiose by melibiase into galactose and glucose; and of melizitose by melizitase into touranose and glucose, touranose yielding glucose also when acted upon by the enzyme touranase.

Commercial Glucose.—The glucose of commerce, which may be regarded as a mixture of grape sugar, maltose and dextrins, is prepared by hydrolysing starch by boiling with a dilute mineral acid. In Europe, potato starch is generally employed; in America, corn starch. The acid employed may be hydrochloric, which gives the best results, or sulphuric, which is used in Germany; sulphuric acid is more readily separated from the product than hydrochloric, since the addition of powdered chalk precipitates it as calcium sulphate, which may be removed by a filter press. The processes of manufacture have much in common, although varying in detail. The following is an outline of the process when hydrochloric acid is used: Starch (“green” starch in America) is made into a “milk” with water, and the milk pumped into boiling dilute acid contained in a closed “converter,” generally made of copper or cast iron; steam is led in at the same time, and the pressure is kept up to about 25 ℔ to the sq. in. When the converter is full the pressure is raised somewhat, and the heating continued until the conversion is complete. The liquid is now run into neutralizing tanks containing sodium carbonate, and, after settling, the supernatant liquid, termed “light liquor,” is run through bag filters and then on to bone-char filters, which have been previously used for the “heavy liquor.” The colourless or amber-coloured filtrate is concentrated to 27° to 28° B., when it forms the “heavy liquor,” just mentioned. This is filtered through fresh bone-char filters, from which it is discharged as a practically colourless liquid. This liquid is concentrated in vacuum pans to a specific gravity of 40° to 44° B., a small quantity of sodium bisulphite solution being added to bleach it, to prevent fermentation, and to inhibit browning. “Syrup glucose” is the commercial name of the product; by continuing the concentration further solid glucose or grape sugar is obtained.

Several brands are recognized: “Mixing glucose” is used by syrup and molasses manufacturers, “jelly glucose” by makers of jellies, “confectioners’ glucose” in confectionery, “brewers’ glucose” in brewing, &c.