Reducing sugars, oxidation

The formation of a red precipitate of copper(I) oxide by reduction of Cu(II) is taken as a positive test for an aldehyde Carbohydrates that give positive tests with Benedict s reagent are termed reducing sugars... 

Aldoses are reducing sugars because they possess an aldehyde function m then-open chain form Ketoses are also reducing sugars Under the conditions of the test ketoses equilibrate with aldoses by way of enediol intermediates and the aldoses are oxidized by the reagent... 

Oxidation with Benedict s reagent (Section 25 19) Sugars that con tain a free hemiacetal function are called reducing sugars They react with copper(ll) sulfate in a sodium citrate/sodium carbonate buffer (Benedict s reagent) to form a red precipitate of copper(l) oxide Used as a qualitative test for reducing sugars... 

Reducing sugar (Section 25 19) A carbohydrate that can be oxidized with substances such as Benedict s reagent In general a carbohydrate with a free hydroxyl group at the anomenc position... 

Ofner Method. This method is for the determination of invert sugar in products with up to 10% invert in the presence of sucrose and is a copper-reduction method that uses Ofner s solution instead of Fehling s. The reduced cuprous oxide is treated with excess standardized iodine, which is black-titrated with thiosulfate using starch indicator. 

Colorimetric Methods. Numerous colorimetric methods exist for the quantitative determination of carbohydrates as a group (8). Among the most popular of these is the phenol—sulfuric acid method of Dubois (9), which rehes on the color formed when a carbohydrate reacts with phenol in the presence of hot sulfuric acid. The test is sensitive for virtually all classes of carbohydrates. Colorimetric methods are usually employed when a very small concentration of carbohydrate is present, and are often used in clinical situations. The Somogyi method, of which there are many variations, rehes on the reduction of cupric sulfate to cuprous oxide and is appHcable to reducing sugars. 

Oxidation of the aldehyde group of an aldose to form a carboxyUc acid or carboxyUc acid anion is often used analytically to determine the amount of reducing sugar. The Benedict and Fehling methods measure the amount of reducing sugar present in a fluid. In these reactions, the oxidant, Cu ", is reduced to Cu". Cu" precipitates as CU2O, which can be measured in a variety of ways. In the ToUens test, Ag" is reduced to Ag. ... 

Carbon and Hydrogen.—Carbon compounds are frequently inflammable, and when heated on platinum foil take fipe or char and burn away. A safer test is to heat the substance with some easily reducible metallic oxide, the oxygen of which forms carbon diovide with the carbon present. Take a piece of soft glass tube about 13 cm. (5 in.) long, and fuse it together at one end. Heat a gram or two of fine copper oxide in a porcelain crucible for a few minutes to drive off the moisture, and let it cool in a desiccator. Mix it with about one-tenth of its bulk of powdered sugar in a mortar. Pour the mixture into the tube, the open end of which is now drawn out into a wide capillary and oeni. at the same time into the form Fig. i. 

Although the Tollens reaction is a useful test for reducing sugars, it doesn t give good yields of aldonic acid products because the alkaline conditions cause decomposition of the carbohydrate. For preparative purposes, a buffered solution of aqueous Br2 is a better oxidant. The reaction is specific for aldoses ketoses are not oxidized by aqueous Br2. 

Figure 9.48 A cyanine dye containing a hydrazide group can be used to label glycans at their reducing end or other reducing sugars, forming a hydrazone linkage. Glycoproteins also can be labeled after periodate oxidation to form aldehyde groups.

---