Dehydroascorbic acid: Difference between revisions

{{short description|Metabolite of vitamin C}}

{{About|the vitamin C metabolite|the omega-3 fatty acid also abbreviated as DHA|Docosahexaenoic acid}}

| verifiedrevid = 450728545

| ImageFile = Dehydroascorbic acid 2.svg

| ImageSize = 100px

| IUPACName = <small>L</small>-''threo''-Hexo-2,3-diulosono-1,4-lactone

| SystematicName = (5''R'')-5-[(1''S'')-1,2-Dihydroxyethyl]oxolane-2,3,4-trione

| IUPHAR_ligand = 4733

| UNII_Ref = {{fdacite|correct|FDA}}

| UNII = Y2Z3ZTP9UM

'''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.<ref name=May1998>

{{Cite journal

|last=May |first=J. M.

|year=1998

|title=Ascorbate function and metabolism in the human erythrocyte

|journal=[[Frontiers in Bioscience]]

|volume=3 |issue= 4|pages=d1–10

|doi=10.2741/a262

|pmid=9405334

|doi-access=free

}}</ref> It is trapped therein by reduction back to ascorbic acid by [[glutathione]] and other [[thiols]].<ref>

{{cite journal

|last1=Welch |first1=R. W.

|last2=Wang |first2=Y.

|last3=Crossman |first3=A. Jr.

|last4=Park |first4=J. B.

|last5=Kirk |first5=K. L.

|last6=Levine |first6=M.

|year=1995

|title=Accumulation of Vitamin C (Ascorbate) and Its Oxidized Metabolite Dehydroascorbic Acid Occurs by Separate Mechanisms

|journal=[[Journal of Biological Chemistry]]

|volume=270 |issue=21 |pages=12584–12592

|doi=10.1074/jbc.270.21.12584

|pmid=7759506

|doi-access=free

}}</ref> The [[Radical (chemistry)|(free) chemical radical]] semidehydroascorbic acid (SDA) also belongs to the group of oxidized ascorbic acids.

==Structure and physiology==

{| width="100" style="font-size: 85%; border: 1px solid #CCCCCC; margin: 0.3em;" border="0" cellspacing="0" cellpadding="2"

|[[Image:Ascorbic acid structure.svg|100px]]

{| width="100" style="font-size: 85%; border: 1px solid #CCCCCC; margin: 0.3em;" border="0" cellspacing="0" cellpadding="2"

|[[Image:Dehydroascorbic acid 2.svg|100px]]

Although sodium-dependent transporters for [[vitamin C]] exists, it is present mainly in specialized cells whereas the [[glucose transporter]]s, most notably [[GLUT1]], transport DHA in most cells,<ref name="MitoGolde" /> where recycling back to ascorbic acid 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|hemiketal]] formation between the 6-OH and the 3-carbonyl groups. Hydration of the 2-carbonyl is also observed.<ref>

{{cite journal

|last1=Kerber|first1=R. C.

|year=2008

|title="As Simple as Possible, but Not Simpler"—The Case of Dehydroascorbic Acid

|journal= Journal of Chemical Education

|volume=85 |issue=9 |pages=1237

|doi=10.1021/ed085p1237

|bibcode=2008JChEd..85.1237K

}}</ref> The lifetime of the stabilized species is commonly said to be about 6 minutes under biological conditions.<ref name=May1998/> Destruction results from irreversible hydrolysis of the lactone bond, with additional degradation reactions following.<ref>

{{cite journal

|last1=Kimoto |first1=E.

|last2=Tanaka |first2=H.

|last3=Ohmoto |first3=T.

|last4=Choami |first4=M.

|year=1993

|title=Analysis of the transformation products of dehydro-L-ascorbic acid by ion-pairing high-performance liquid chromatography

|journal=Analytical Biochemistry

|volume=214 |issue=1 |pages=38–44

|doi=10.1006/abio.1993.1453

|pmid=8250252

}}</ref> Crystallization of solutions of DHA gives a pentacyclic dimer structure of indefinite stability. Recycling of vitamin C via active transport of DHA into cells, followed by reduction and reuse, mitigates the inability of humans to synthesize it from glucose.<ref>

{{cite journal

|last1=Montel-Hagen |first1=A.

|last2=Kinet |first2=S.

|last3=Manel |first3=N.

|last4=Mongellaz |first4=C.

|last5=Prohaska |first5=R.

|last6=Battini |first6=J. L.

|last7=Delaunay |first7=J.

|last8=Sitbon |first8=M.

|last9=Taylor |first9=N.

|year=2008

|title=Erythrocyte Glut1 triggers dehydroascorbic acid uptake in mammals unable to synthesize vitamin C

|journal=Cell

|volume=132 |issue=6 |pages=1039–48

|doi=10.1016/j.cell.2008.01.042

|pmid=18358815

|doi-access=free

}}</ref>

[[Image:Dehydroascorbic acid.svg|frame|none|link=|Hydration equilibria of DHA - center hemiketal structure is the predominant species in aqueous solutions.<ref>{{Cite journal |last1=Koliou |first1=Eleftheria K. |last2=Ioannou |first2=Panayiotis V. |date=February 2005 |title=Preparation of dehydro-l-ascorbic acid dimer by air oxidation of l-ascorbic acid in the presence of catalytic amounts of copper(II) acetate and pyridine |url=https://linkinghub.elsevier.com/retrieve/pii/S000862150400494X |journal=Carbohydrate Research |language=en |volume=340 |issue=2 |pages=315–318 |doi=10.1016/j.carres.2004.11.015|pmid=15639252 }}</ref>]]

Vitamin C accumulates in [[mitochondria]], where most of the [[free radical]]s are produced, by entering as DHA through the glucose transporter GLUT10. Ascorbic acid protects the [[mitochondrial genome]] and [[Mitochondrial membrane#Mitochondrion structure|membrane]].<ref name="MitoGolde">

|last1=Lee |first1=Y. C.

|last2=Huang |first2=H. Y.

|last3=Chang |first3=C. J.

|last4=Cheng |first4=C. H.

|last5=Chen |first5=Y. T.

|year=2010

|title=Mitochondrial GLUT10 facilitates dehydroascorbic acid import and protects cells against oxidative stress: Mechanistic insight into arterial tortuosity syndrome

|journal=Human Molecular Genetics

|volume=19 |issue=19 |pages=3721–33

|doi=10.1093/hmg/ddq286

|pmid=20639396

|doi-access=free

}}</ref>

Vitamin C does not pass from the bloodstream into the [[brain]], although the brain is one of the organs that have<!--keep this predicate PLURAL: subject-pronoun "that," whose antecedent is "organs," is PLURAL--> the greatest concentration of vitamin C. Instead, DHA is transported through the [[blood–brain barrier]] via [[GLUT1|GLUT1 transporters]], and then reduced back to ascorbic acid.<ref name="ascorBBB">

{{cite journal

|last1=Huang|first1=J.

|last2=Agus |first2=D. B.

|last3=Winfree |first3=C. J.

|last4=Kiss |first4=S.

|last5=Mack |first5=W. J.

|last6=McTaggart |first6=R. A.

|last7=Choudhri |first7=T. F.

|last8=Kim |first8=L. J.

|last9=Mocco |first9=J.

|last10=Pinsky |first10=D. J.

|last11=Fox |first11=W. D.

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|last14=Golde |first14=D. W.

|last15=Connolly |first15=E. S. Jr |author15-link=E. Sander Connolly

|year=2001

|title=Dehydroascorbic acid, a blood–brain barrier transportable form of vitamin C, mediates potent cerebroprotection in experimental stroke

|journal=Proceedings of the National Academy of Sciences of the United States of America

|volume=98 |issue=20 |pages=11720–11724

|doi=10.1073/pnas.171325998

|pmc=58796

|pmid=11573006

|bibcode=2001PNAS...9811720H

|doi-access=free

}}</ref>

Dehydroascorbic acid has been used as a vitamin C dietary supplement.<ref>{{cite web | url = http://lpi.oregonstate.edu/ss01/bioavailability.html | title = The Bioavailability of Different Forms of Vitamin C | access-date = 2010-11-10 | last = Higdon | first = Jane | date = May 2001 | publisher = The Linus Pauling Institute}}</ref>

As a cosmetic ingredient, dehydroascorbic acid is used to enhance the appearance of the skin.<ref>{{Citation

| title = Topical Dehydroascorbic Acid (Oxidized Vitamin C) Permeates Stratum Corneum More Rapidly Than Ascorbic Acid

| url = https://www.researchgate.net/publication/225274699

| year = 2012

| author = Kitt, D.Q.

| access-date = 2012-07-31

}}</ref> It may be used in a process for [[Perm (hairstyle)|permanent waving of hair]]<ref name="US6506373">[http://patft.uspto.gov/netacgi/nph-Parser?Sect1=PTO1&Sect2=HITOFF&d=PALL&p=1&u=%2Fnetahtml%2FPTO%2Fsrchnum.htm&r=1&f=G&l=50&s1=6506373.PN.&OS=PN/6506373&RS=PN/6506373 US Patent 6,506,373] {{Webarchive|url=https://web.archive.org/web/20201225063323/http://patft.uspto.gov/netacgi/nph-Parser?Sect1=PTO1&Sect2=HITOFF&d=PALL&p=1&u=%2Fnetahtml%2FPTO%2Fsrchnum.htm&r=1&f=G&l=50&s1=6506373.PN.&OS=PN%2F6506373&RS=PN%2F6506373 |date=2020-12-25 }} (issued January 14, 2003)</ref> and in a process for [[sunless tanning]] of skin.<ref name="LOreal">[http://appft1.uspto.gov/netacgi/nph-Parser?Sect1=PTO1&Sect2=HITOFF&d=PG01&p=1&u=%2Fnetahtml%2FPTO%2Fsrchnum.html&r=1&f=G&l=50&s1=%2220100221203%22.PGNR.&OS=DN/20100221203&RS=DN/20100221203 U.S. Patent Application No. 10/685,073] Publication No. 20100221203 (published September 2, 2010)</ref>

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.<ref name="cellculture">

|vauthors=Heaney ML, Gardner JR, Karasavvas N, Golde DW, Scheinberg DA, Smith EA, O'Conner OA |title=Vitamin C antagonizes the cytotoxic effects of antineoplastic drugs

|url= |journal=Cancer Research

|doi=10.1158/0008-5472.CAN-08-1490|pmc=3695824

}}</ref>

|vauthors=Furuya A, Uozaki M, Yamasaki H, Arakawa T, Arita M, Koyama AH |title=Antiviral effects of ascorbic and dehydroascorbic acids in vitro

|doi=10.3892/ijmm_00000053|doi-access=free

}}</ref> 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.<ref name=Ericsson>[http://free.patentfetcher.com/GetPatentPDF.php?f=Pats/US/30/65/US3065139.pdf Ericsson, Sten et al. "Anti Infectant Topical Preparations." U.S. Patent 3,065,139, filed November 9, 1954 and issued November 20, 1962]</ref><ref name=Fine>[http://free.patentfetcher.com/GetPatentPDF.php?f=Pats/US/52/98/US5298237.pdf 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]</ref> 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.<ref name="Fine" /><ref name=herpes>{{cite journal | pmid = 8540748 | volume=27 | issue=3 | title=Topical treatment of recurrent mucocutaneous herpes with ascorbic acid-containing solution |vauthors=Hovi T, Hirvimies A, Stenvik M, Vuola E, Pippuri R | journal=Antiviral Res | pages=263–70 | doi=10.1016/0166-3542(95)00010-j| year=1995 }}</ref> Ascoxal solution has also been tested with positive results as a treatment for recurrent mucocutaneous herpes,<ref name="herpes" /> and as a mucolytic agent in acute and chronic pulmonary disease such as emphysema, bronchitis, and asthma by aerosol inhalation.<ref>{{cite journal |vauthors=Fisher AJ, Ten Pas RH | year = 1966 | title = Clinical evaluation of Ascoxal: a new mucolytic agent | journal = Anesthesia and Analgesia | volume = 45 | issue = 5| pages = 531–534 | doi=10.1213/00000539-196645050-00003| pmid = 5330913 | doi-access = free }}</ref>

{{Reflist|30em}}

* {{cite journal |vauthors=Nualart F, Rivas C, Montecinos V, Godoy A, Guaiquil V, Golde D, Vera J |title=Recycling of vitamin C by a bystander effect |journal=J Biol Chem |volume=278 |issue=12 |pages=10128–33 |year=2003 |pmid=12435736 |doi=10.1074/jbc.M210686200 |doi-access=free }}

==External links==

*{{Commons category-inline}}

[[Category:Vitamin C]]

[[Category:Diketones]]