Ketose

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Fructose, an example of a ketose. The ketone group is the double-
bonded oxygen. DL-Fructose.svg
Fructose, an example of a ketose. The ketone group is the double-
bonded oxygen.

In organic chemistry, a ketose is a monosaccharide containing one ketone (>C=O) group per molecule. [1] [2] The simplest ketose is dihydroxyacetone ((CH2OH)2C=O), which has only three carbon atoms. It is the only ketose with no optical activity. All monosaccharide ketoses are reducing sugars, because they can tautomerize into aldoses via an enediol intermediate, and the resulting aldehyde group can be oxidised, for example in the Tollens' test or Benedict's test. [3] Ketoses that are bound into glycosides, for example in the case of the fructose moiety of sucrose, are nonreducing sugars. [3]

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Chemistry

Ketoses and aldoses can be chemically differentiated through Seliwanoff's test, where the sample is heated with acid and resorcinol. [4] The test relies on the dehydration reaction which occurs more quickly in ketoses, so that while aldoses react slowly, producing a light pink color, ketoses react more quickly and strongly to produce a dark red color. Ketoses can isomerize to aldoses through the Lobry-de Bruyn-van Ekenstein transformation.

Examples of ketoses

Family tree of D-ketoses up to hexoses: dihydroxyacetone (1); D-erythrulose (2); D-ribulose (3a); D-xylulose (3b); D-psicose (4a); D-fructose (4b); D-sorbose (4c); D-tagatose (4d) Family tree of d-ketoses.svg
Family tree of D-ketoses up to hexoses: dihydroxyacetone (1); D-erythrulose (2); D-ribulose (3a); D-xylulose (3b); D-psicose (4a); D-fructose (4b); D-sorbose (4c); D-tagatose (4d)

All ketoses listed here are 2-ketoses, in other words, the carbonyl group is on the second carbon atom from the end:

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<span class="mw-page-title-main">Carbohydrate</span> Organic compound that consists only of carbon, hydrogen, and oxygen

A carbohydrate is a biomolecule consisting of carbon (C), hydrogen (H) and oxygen (O) atoms, usually with a hydrogen–oxygen atom ratio of 2:1 and thus with the empirical formula Cm(H2O)n, which does not mean the H has covalent bonds with O. However, not all carbohydrates conform to this precise stoichiometric definition, nor are all chemicals that do conform to this definition automatically classified as carbohydrates.

<span class="mw-page-title-main">Glucose</span> Naturally produced monosaccharide

Glucose is a sugar with the molecular formula C6H12O6. Glucose is overall the most abundant monosaccharide, a subcategory of carbohydrates. Glucose is mainly made by plants and most algae during photosynthesis from water and carbon dioxide, using energy from sunlight, where it is used to make cellulose in cell walls, the most abundant carbohydrate in the world.

Monosaccharides, also called simple sugars, are the simplest forms of sugar and the most basic units (monomers) from which all carbohydrates are built. Simply, this is the structural unit of carbohydrates.

In chemistry, a pentose is a monosaccharide with five carbon atoms. The chemical formula of many pentoses is C
5
H
10
O
5
, and their molecular weight is 150.13 g/mol.

<span class="mw-page-title-main">Hexose</span> 6-Carbon simple sugar

In chemistry, a hexose is a monosaccharide (simple sugar) with six carbon atoms. The chemical formula for all hexoses is C6H12O6, and their molecular weight is 180.156 g/mol.

Benedict's reagent is a chemical reagent and complex mixture of sodium carbonate, sodium citrate, and copper(II) sulfate pentahydrate. It is often used in place of Fehling's solution to detect the presence of reducing sugars. The presence of other reducing substances also gives a positive result. Such tests that use this reagent are called the Benedict's tests. A positive test with Benedict's reagent is shown by a color change from clear blue to brick-red with a precipitate.

An aldose is a monosaccharide with a carbon backbone chain with a carbonyl group on the endmost carbon atom, making it an aldehyde, and hydroxyl groups connected to all the other carbon atoms. Aldoses can be distinguished from ketoses, which have the carbonyl group away from the end of the molecule, and are therefore ketones.

<span class="mw-page-title-main">Triose</span> Sugar containing three carbon atoms

A triose is a monosaccharide, or simple sugar, containing three carbon atoms. There are only three possible trioses: the two enantiomers of glyceraldehyde, which are aldoses; and dihydroxyacetone, a ketose which is symmetrical and therefore has no enantiomers.

<span class="mw-page-title-main">Fehling's solution</span> Chemical test for the reducibility of a sugar

In organic chemistry, Fehling's solution is a chemical reagent used to differentiate between water-soluble carbohydrate and ketone functional groups, and as a test for reducing sugars and non-reducing sugars, supplementary to the Tollens' reagent test. The test was developed by German chemist Hermann von Fehling in 1849.

In carbohydrate chemistry, a pair of anomers is a pair of near-identical stereoisomers or diastereomers that differ at only the anomeric carbon, the carbon that bears the aldehyde or ketone functional group in the sugar's open-chain form. However, in order for anomers to exist, the sugar must be in its cyclic form, since in open-chain form, the anomeric carbon is planar and thus achiral. More formally stated, then, an anomer is an epimer at the hemiacetal/hemiketal carbon in a cyclic saccharide. Anomerization is the process of conversion of one anomer to the other. As is typical for stereoisomeric compounds, different anomers have different physical properties, melting points and specific rotations.

<span class="mw-page-title-main">Reducing sugar</span> Sugars that contain free OH group at the anomeric carbon atom

A reducing sugar is any sugar that is capable of acting as a reducing agent. In an alkaline solution, a reducing sugar forms some aldehyde or ketone, which allows it to act as a reducing agent, for example in Benedict's reagent. In such a reaction, the sugar becomes a carboxylic acid.

A heptose is a monosaccharide with seven carbon atoms.

Glycal is a name for cyclic enol ether derivatives of sugars having a double bond between carbon atoms 1 and 2 of the ring. The term "glycal" should not be used for an unsaturated sugar that has a double bond in any position other than between carbon atoms 1 and 2.

<span class="mw-page-title-main">Transketolase</span> Enzyme involved in metabolic pathways

Transketolase is an enzyme that, in humans, is encoded by the TKT gene. It participates in both the pentose phosphate pathway in all organisms and the Calvin cycle of photosynthesis. Transketolase catalyzes two important reactions, which operate in opposite directions in these two pathways. In the first reaction of the non-oxidative pentose phosphate pathway, the cofactor thiamine diphosphate accepts a 2-carbon fragment from a 5-carbon ketose (D-xylulose-5-P), then transfers this fragment to a 5-carbon aldose (D-ribose-5-P) to form a 7-carbon ketose (sedoheptulose-7-P). The abstraction of two carbons from D-xylulose-5-P yields the 3-carbon aldose glyceraldehyde-3-P. In the Calvin cycle, transketolase catalyzes the reverse reaction, the conversion of sedoheptulose-7-P and glyceraldehyde-3-P to pentoses, the aldose D-ribose-5-P and the ketose D-xylulose-5-P.

<span class="mw-page-title-main">Sugar acid</span> Sugar molecule with an –OH group at the end(s) of the carbon chain

In organic chemistry, a sugar acid or acidic sugar is a monosaccharide with a carboxyl group at one end or both ends of its chain.

The Kiliani–Fischer synthesis, named for German chemists Heinrich Kiliani and Emil Fischer, is a method for synthesizing monosaccharides. It proceeds via synthesis and hydrolysis of a cyanohydrin, followed by reduction of the intermediate acid to the aldehyde, thus elongating the carbon chain of an aldose by one carbon atom while preserving stereochemistry on all the previously present chiral carbons. The new chiral carbon is produced with both stereochemistries, so the product of a Kiliani–Fischer synthesis is a mixture of two diastereomeric sugars, called epimers. For example, D-arabinose is converted to a mixture of D-glucose and D-mannose.

In carbohydrate chemistry, the Lobry de Bruyn–Van Ekenstein transformation also known as the Lobry de Bruyn–Alberda van Ekenstein transformation is the base or acid catalyzed transformation of an aldose into the ketose isomer or vice versa, with a tautomeric enediol as reaction intermediate. Ketoses may be transformed into 3-ketoses, etcetera. The enediol is also an intermediate for the epimerization of an aldose or ketose.

<span class="mw-page-title-main">Seliwanoff's test</span> Chemical test

Seliwanoff’s test is a chemical test which distinguishes between aldose and ketose sugars. If the sugar contains a ketone group, it is a ketose. If a sugar contains an aldehyde group, it is an aldose. This test relies on the principle that, when heated, ketoses are more rapidly dehydrated than aldoses. It is named after Theodor Seliwanoff, the chemist who devised the test. When added to a solution containing ketoses, a red color is formed rapidly indicating a positive test. When added to a solution containing aldoses, a slower forming light pink is observed instead.

Monosaccharide nomenclature is the naming system of the building blocks of carbohydrates, the monosaccharides, which may be monomers or part of a larger polymer. Monosaccharides are subunits that cannot be further hydrolysed in to simpler units. Depending on the number of carbon atom they are further classified into trioses, tetroses, pentoses, hexoses etc., which is further classified in to aldoses and ketoses depending on the type of functional group present in them.

References

  1. Lindhorst, Thisbe K. (2007). Essentials of Carbohydrate Chemistry and Biochemistry (1st ed.). Wiley-VCH. ISBN   978-3-527-31528-4.
  2. Robyt, John F. (1997). Essentials of Carbohydrate Chemistry (1st ed.). Springer. ISBN   0-387-94951-8.
  3. 1 2 McMurry, John E. (2010-01-01). Organic Chemistry: With Biological Applications. Cengage Learning. p. 880. ISBN   978-0495391449.
  4. "Seliwanoff's Test". Harper College. Archived from the original on 2017-12-16. Retrieved 2011-07-10.