Jump to content

Chemistry of ascorbic acid

From Wikipedia, the free encyclopedia

This is an old revision of this page, as edited by 75.35.79.57 (talk) at 03:39, 22 June 2007 (→‎Uses: wlks). The present address (URL) is a permanent link to this revision, which may differ significantly from the current revision.

Template:Chembox new

This article deals with the molecular aspects of ascorbic acid. For information about its purpose in nutrition, see Vitamin C.

Ascorbic acid is an organic acid with antioxidant properties. Its appearance is white to light yellow crystals or powder. It is water soluble. The L-enantiomer of ascorbic acid is commonly known as vitamin C. The name is derived from a- and scorbuticus (Scurvy) as a shortage of this molecule may lead to scurvy. In 1937 the Nobel Prize for chemistry was awarded to Walter Haworth for his work in determining the structure of ascorbic acid (shared with Paul Karrer, who received his award for work on vitamins), and the prize for Physiology or Medicine that year went to Albert Szent-Györgyi for his studies of the biological functions of L-ascorbic acid. At the time of its discovery in the 1920s it was called hexuronic acid by some researchers.[1]

Chemistry

Acidity

Ascorbic acid behaves as a vinylogous carboxylic acid, where the double bond ("vinyl") transmits electron pairs between the hydroxyl and the carbonyl. There are two resonance structures for the deprotonated form, differing in the position of the double bond.

Another way to look at ascorbic acid is to consider it as an enol. The deprotonated form is an enolate, which are usually strongly basic. However, the adjacent double bond stabilizes the deprotonated form.

Movement of electron pairs in deprotonation


Tautomerism

Attack of ascorbic enol on proton to give 1,3-diketone

Ascorbic acid also rapidly interconverts into two unstable diketone tautomers by proton transfer, although it is the most stable in the enol form. The proton of the enol is lost, and reacquired by electrons from the double bond, to produce a diketone. This is an enol reaction. There are two possible forms, 1,2-diketone and 1,3-diketone.

Determination

The concentration of a solution of ascorbic acid can be determined in many ways, the most common ways involving titration with an oxidizing agent.

DCPIP

A commonly used oxidising agent is the dye 2,6-dichlorophenol-indophenol, or DCPIP for short. The blue dye is run into the ascorbic acid solution until a faint pink colour persists for 15 seconds.

Iodine

Another method involves using iodine and a starch indicator where iodine reacts with ascorbic acid and when all the ascorbic acid has reacted the iodine is then in excess, forming a blue-black complex with the starch indicator. This indicates the end point of the titration. Alternatively, ascorbic acid can be reacted with iodine in excess, followed by back titration with sodium thiosulfate while using starch as an indicator.

Iodate and iodine

The above method involving iodine requires making up and standardising the iodine solution. One way round this is to generate the iodine in the presence of the ascorbic acid by the reaction of iodate and iodide ion in acid solution.

N-Bromosuccinimide

A much less common oxidising agent is N-bromosuccinimide, (NBS). In this titration the NBS oxidises the ascorbic acid (in the presence of potassium iodide and starch). When the NBS is in excess (i.e. the reaction is complete) the NBS liberates the iodine from the potassium iodide which then forms the blue/black complex with starch, indicating the end point of the titration.

Uses

Ascorbic acid is easily oxidized and so is used as a reductant in photographic developer solutions (among others) and as a preservative.

Exposure to oxygen, metals, light and heat destroy ascorbic acid, so it must be stored in dark and cold and not in a metal container.

The oxidized form of ascorbic acid is known as dehydroascorbic acid.

The L-enantiomer of ascorbic acid is also known as vitamin C. The name "ascorbic" comes from its property of preventing and curing scurvy. Primates, including humans, and a few other species in all divisions of the animal kingdom, notably the guinea pig, have lost the ability to synthesize ascorbic acid and must obtain it in their food.

Ascorbic acid and its sodium, potassium, and calcium salts are commonly used as antioxidant food additives. These compounds are water soluble and thus cannot protect fats from oxidation: For this purpose, the fat-soluble esters of ascorbic acid with long-chain fatty acids (ascorbyl palmitate or ascorbyl stearate) can be used as food antioxidants. Eighty percent of the world's supply of ascorbic acid is produced in China. [2]

The relevant European food additive E numbers are:

  1. E300 ascorbic acid,
  2. E301 sodium ascorbate,
  3. E302 calcium ascorbate,
  4. E303 potassium ascorbate,
  5. E304 fatty acid esters of ascorbic acid (i) ascorbyl palmitate (ii) ascorbyl stearate.

It can be added to water that has been treated with iodine to make it potable, neutralizing the unpleasant iodine taste.

Antioxidant mechanism

Ascorbate acts as an antioxidant by being itself available for energetically favourable oxidation. Many oxidants (typically, reactive oxygen species) such as the hydroxyl radical (formed from hydrogen peroxide), contain an unpaired electron and thus are highly reactive and damaging to humans and plants at the molecular level. This is due to their interaction with nucleic acid, proteins and lipids. Reactive oxygen species oxidize (take electrons from) ascorbate first to monodehydroascorbate and then dehydroascorbate. The reactive oxygen species are reduced to water while the oxidized forms of ascorbate are relatively stable and unreactive, and do not cause cellular damage.

See also

References

  1. ^ Joseph Louis Svirbelf, Albert Szent-Gyorgyi The Chemical Nature Of Vitamin C, April 25th, 1932. Part of the National Library of Medicine collection. Accessed January 2007
  2. ^ Washington Post, Tainted Chinese Imports Common, published May 20, 2007
  • Clayden, Greeves, Warren, Wothers. Organic Chemistry. Oxford University Press (2001), ISBN 0-19-850346-6.
  • Derek Denby Chemistry Review, May 1996

Template:ChemicalSources

Retrieved from "https://en.wikipedia.org/w/index.php?title=Chemistry_of_ascorbic_acid&oldid=139817929"