Dehydroascorbic acid

Dehydroascorbic acid
Names
IUPAC name
(5R)-5-[(1S)-1,2-dihydroxyethyl]furan-2,3,4(5H)-trione
Identifiers
490-83-5 YesY
3D model (Jmol) Interactive image
ChEBI CHEBI:27956 YesY
ChemSpider 389547 YesY
ECHA InfoCard 100.007.019
4733
PubChem 440667
Properties
C6H6O6
Molar mass 174.11 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Dehydroascorbic acid (DHA) is an oxidized form of ascorbic acid (vitamin C). It is actively imported into the endoplasmic reticulum of cells via glucose transporters. It is trapped therein by reduction back to ascorbate by glutathione and other thiols.[1] The (free) chemical radical semidehydroascorbic acid (SDA) also belongs to the group of oxidized ascorbic acids.

Structure and Physiology

Top: ascorbic acid
(reduced form of vitamin C)
Bottom: dehydroascorbic acid
(nominal oxidized form of vitamin C)

Although a sodium-dependent transporter for vitamin C exists, it is present mainly in specialized cells, whereas the glucose transporters, the most notable being GLUT1, transport Vitamin C (in its oxidized form, DHA)[2] in most cells, where recycling back to ascorbate generates the necessary enzyme cofactor and intracellular antioxidant, (see Transport to mitochondria).

The structure shown here for DHA is the commonly shown textbook structure. This 1,2,3-tricarbonyl is too electrophilic to survive more than a few milliseconds in aqueous solution, however. The actual structure shown by spectroscopic studies is the result of rapid hemiacetal formation between the 6-OH and the 3-carbonyl groups. Hydration of the 2-carbonyl is also observed.[3] The lifetime of the stabilized species is commonly said to be about 6 minutes under biological conditions.[4] Destruction results from irreversible hydrolysis of the ester bond, with additional degradation reactions following.[5] Crystallization of solutions of DHA gives a pentacyclic dimer structure of indefinite stability. Recycling of ascorbate via active transport of DHA into cells, followed by reduction and reuse, mitigates the inability of humans to synthesize it from glucose.[6]

Transport to mitochondria

Vitamin C accumulates in mitochondria, where most of the free radicals are produced, by entering as DHA through the glucose transporters, GLUT10. Ascorbic acid protects the mitochondrial genome and membrane.[2]

Transport to the brain

Vitamin C does not pass from the bloodstream into the brain, although the brain is one of the organs that have the greatest concentration of vitamin C. Instead, DHA is transported through the blood–brain barrier via GLUT1 transporters, and then converted back to ascorbate.[7]

Use

Dehydroascorbic acid has been used as a vitamin C dietary supplement.[8]

As a cosmetic ingredient, dehydroascorbic acid is used to enhance the appearance of the skin.[9] It may be used in a process for permanent waving of hair[10] and in a process for sunless tanning of skin.[11]

In a cell culture growth medium, dehydroascorbic acid has been used to assure the uptake of vitamin C into cell types that do not contain ascorbic acid transporters.[12]

As a pharmaceutical agent, some research has suggested that administration of dehydroascorbic acid may confer protection from neuronal injury following an ischemic stroke.[7] The literature contains many reports on the antiviral effects of vitamin C,[13] and one study suggests dehydroascorbic acid has stronger antiviral effects and a different mechanism of action than ascorbic acid.[14] Solutions in water containing ascorbic acid and copper ions and/or peroxide, resulting in rapid oxidation of ascorbic acid to dehydroascorbic acid, have been shown to possess powerful but short-lived antimicrobial, antifungal, and antiviral properties, and have been used to treat gingivitis, periodontal disease, and dental plaque.[15][16] A pharmaceutical product named Ascoxal is an example of such a solution used as a mouth rinse as an oral mucolytic and prophylactic agent against gingivitis.[16][17] Ascoxal solution has also been tested with positive results as a treatment for recurrent mucocutaneous herpes,[17] and as a mucolytic agent in acute and chronic pulmonary disease such as emphysema, bronchitis, and asthma by aerosol inhalation.[18]

References

  1. ↑ Welch, R. W.; Wang, Y.; CrossmanJr., A.; Park, J. B.; Kirk, K. L.; Levine, M. (26 May 1995). "Accumulation of Vitamin C (Ascorbate) and Its Oxidized Metabolite Dehydroascorbic Acid Occurs by Separate Mechanisms". Journal of Biological Chemistry. 270 (21): 12584–12592. doi:10.1074/jbc.270.21.12584. PMID 7759506.
  2. 1 2 Yi-Ching Lee; Hsun-Yi Huang; Chia-Jung Chang; Chao-Hung Cheng; Yuan-Tsong Chen (2010). "Mitochondrial GLUT10 facilitates dehydroascorbic acid import and protects cells against oxidative stress: mechanistic insight into arterial tortuosity syndrome" (PDF). Human Molecular Genetics. 19 (19): 3721–3733. doi:10.1093/hmg/ddq286.
  3. ↑ Kerber, R.C.; "'As Simple as Possible, but not Simpler' -- The Case of Dehydroascorbic Acid," J. Chem. Ed. 85 (2008) 1237-1242.
  4. ↑ May, J.M.; "Ascorbate Function and Metabolism in the Human Erythrocyte," Frontiers in Bioscience, 3 (1981) d1-10.
  5. ↑ Kimoto, E.; Tanaka, H.; Ohmoto, T.; Choami, M.; "Analysis of the Transformation Products of Dehydro-L-Ascorbic Acid by Ion-Pairing High-Performance Liquid Chromatography," Anal. Biochem. 214 (1993) 38-44.
  6. ↑ Montel-Hagen, A.; Kinet, S.; Manel, N.; Mongellaz, C.; Prohaska,R.; Battini, J.L.; Delaunay,J.; Sitbon, M.; Taylor, N.; "Erythrocyte GLUT1 triggers Dehydroascorbic Acid Uptake in Mammals unable to Synthesize Vitamin C," Cell 132 (2008) 1039-48.
  7. 1 2 Huang J; Agus DB; Winfree CJ; Kiss S; Mack WJ; McTaggart RA; Choudhri TF; Kim LJ; Mocco J; Pinsky DJ; Fox WD; Israel RJ; Boyd TA; Golde DW; Connolly ES Jr. (2001). "Dehydroascorbic acid, a blood–brain barrier transportable form of vitamin C, mediates potent cerebroprotection in experimental stroke". Proceedings of the National Academy of Sciences. 98 (20): 11720–11724. doi:10.1073/pnas.171325998. PMC 58796Freely accessible. PMID 11573006.
  8. ↑ Higdon, Jane (May 2001). "The Bioavailability of Different Forms of Vitamin C". The Linus Pauling Institute. Retrieved 2010-11-10.
  9. ↑ Kitt, D.Q. (2012), Topical Dehydroascorbic Acid (Oxidized Vitamin C) Permeates Stratum Corneum More Rapidly Than Ascorbic Acid, retrieved 2012-07-31
  10. ↑ US Patent 6,506,373 (issued Jan. 14, 2003)
  11. ↑ U.S. Patent Application No. 10/685,073 Publication No. 20100221203 (published Sept. 2, 2010)
  12. ↑ Heaney ML, Gardner JR, Karasavvas N, Golde DW, Scheinberg DA, Smith EA, O'Conner OA (2008). "Vitamin C antagonizes the cytotoxic effects of antineoplastic drugs". Cancer Research. 68 (19): 8031–8038. doi:10.1158/0008-5472.CAN-08-1490. PMID 18829561.
  13. ↑ Jariwalla, R.J. & Harakeh S. (1997). Mechanisms underlying the action of vitamin C in viral and immunodeficiency disease. In L. Packer & J. Fuchs (Eds.), Vitamin C in health and disease (pp. 309-322). New York:Marcell Dekker, Inc.
  14. ↑ Furuya A, Uozaki M, Yamasaki H, Arakawa T, Arita M, Koyama AH (2008). "Antiviral effects of ascorbic and dehydroascorbic acids in vitro". International Journal of Molecular Medicine. 22 (4): 541–545. doi:10.3892/ijmm_00000053. PMID 18813862.
  15. ↑ Ericsson, Sten et al. “Anti Infectant Topical Preparations.” U.S. Patent 3,065,139, filed Nov. 9, 1954 and issued Nov. 20, 1962
  16. 1 2 Fine, Daniel. “Gel composition for reduction of gingival inflammation and retardation of dental plaque.” U.S Patent 5,298,237, filed Jan.24, 1992 and issued March 29, 1994
  17. 1 2 Hovi T, et al. Topical treatment of recurrent mucocutaneous herpes with ascorbic acid-containing solution. Antiviral Research 27 (1995) 263-270
  18. ↑ Fisher AJ and Ten Pas RH. Clinical evaluation of Ascoxal: a new mucolytic agent. Anesthesia and Analgesia 45(5) 531-534 (1966)

Further reading

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