Jump to content

Catechin: Difference between revisions

From Wikipedia, the free encyclopedia
Browse history interactively
← Previous editNext edit →
Content deleted Content added
VisualWikitext
BG19bot (talk | contribs)
1,005,055 edits
m WP:CHECKWIKI error fix. Syntax fixes. Do general fixes if a problem exists. -
Ggux (talk | contribs)
347 edits
Assisted by Citation bot Added medicinal use with better references and effect on immune system
Line 194: Line 194:
==== Taste ====
==== Taste ====
The taste associated with monomeric (+)-catechin or (-)-epicatechin is described as not exactly [[astringent]], nor exactly bitter.<ref>{{cite journal |doi=10.1016/S0950-3293(98)00049-4 |title=Oral sensations associated with the flavan-3-ols (+)-catechin and (−)-epicatechin |year=1999 |last1=Kielhorn |first1=S |last2=Thorngate Iii |first2=J.H |journal=Food Quality and Preference |volume=10 |issue=2 |pages=109–116}}</ref>
The taste associated with monomeric (+)-catechin or (-)-epicatechin is described as not exactly [[astringent]], nor exactly bitter.<ref>{{cite journal |doi=10.1016/S0950-3293(98)00049-4 |title=Oral sensations associated with the flavan-3-ols (+)-catechin and (−)-epicatechin |year=1999 |last1=Kielhorn |first1=S |last2=Thorngate Iii |first2=J.H |journal=Food Quality and Preference |volume=10 |issue=2 |pages=109–116}}</ref>

==Medicinal use==
(+)-catechin has been used to treat acute [[viral hepatitis]] <ref>{{cite book |last=Bode |first=JC |date=1987 |title=Assessment and Management of Hepatobiliary Disease |location= Berlin |publisher=Springer-Verlag |page= 371|isbn=978-3-642-72631-6|doi=10.1007/978-3-642-72631-6}}</ref> and was marketed under the name Catergen by Zyma (now [[Novartis]]). Severe side effects (see [[Catechin#Immune function]]) lead to the withdrawal of the drug.


== Metabolism ==
== Metabolism ==
Line 221: Line 224:


=== Research ===
=== Research ===
Plasma catechin metabolites are present as conjugated forms and mainly constituted by [[glucuronic acid|glucuronidated]] derivatives. In the liver, the concentrations of catechin derivatives are lower than in plasma, and no accumulation is observed when the rats are adapted for 14 days to the supplemented diets. The hepatic metabolites are intensively methylated (90–95%), but in contrast to plasma, some free aglycones can be detected.<ref>{{cite journal | doi = 10.1016/S0891-5849(99)00159-8 | title = Comparison of the bioavailability of quercetin and catechin in rats | year = 1999 | last1 = Manach | first1 = Claudine | last2 = Texier | first2 = Odile | last3 = Morand | first3 = Christine | last4 = Crespy | first4 = Vanessa | last5 = Régérat | first5 = Françoise | last6 = Demigné | first6 = Christian | last7 = Rémésy | first7 = Christian | journal = Free Radical Biology and Medicine | volume = 27 | issue = 11–12 | pages = 1259–66 | pmid = 10641719}}</ref> Rats fed with (+)-catechin and (-)-epicatechin exhibit (+)-catechin 5-O-β-glucuronide and (-)-epicatechin 5-O-β-glucuronide in their body fluids.<ref>{{cite journal |vauthors=Harada M, Kan Y, Naoki H |title=Identification of the major antioxidative metabolites in biological fluids of the rat with ingested (+)-catechin and (-)-epicatechin |journal=Biosci. Biotechnol. Biochem. |volume=63 |issue=6 |pages=973–7 |date=June 1999 |pmid=10427682 |doi=10.1271/bbb.63.973|display-authors=etal}}</ref> The primary metabolite of (+)-catechin in rat plasma is a glucuronide in the nonmethylated form. In contrast, the primary metabolites of (-)-epicatechin in rat plasma are glucuronide and sulfoglucuronide in nonmethylated forms, and sulfate in the 3'-O-methylated forms (3'OMC).<ref>{{cite journal |vauthors=Baba S, Osakabe N, Natsume M, Muto Y, Takizawa T, Terao J |title=In vivo comparison of the bioavailability of (+)-catechin, (-)-epicatechin and their mixture in orally administered rats |journal=J. Nutr. |volume=131 |issue=11 |pages=2885–91 |date=November 2001 |pmid=11694613 |url=http://jn.nutrition.org/cgi/pmidlookup?view=long&pmid=11694613}}</ref> The recent use of radiocarbon-labeled epicatechin [14C-labeled (−)-epicatechin] demonstrated significant species-dependent differences in the metabolism of (-)-epicatechin in rat, mouse and human.<ref name="Ottaviani_2016">{{cite journal|last1=Ottaviani|first1=Javier|title=The metabolome of [2-14C] (−)-epicatechin in humans: implications for the assessment of efficacy, safety, and mechanisms of action of polyphenolic bioactives|journal=Nature-Scientific Reports|year=2016|volume=29034|issue=6|doi=10.1038/srep29034|url=http://www.ncbi.nlm.nih.gov/pmc/articles/PMC4929566/}}</ref> Catechin is absorbed into intestinal cells and metabolized extensively because no native catechin can be detected in plasma from the mesenteric vein.<ref name=lpi/> Additional methylation and sulfation occur in the liver, and glucuronide or sulfate conjugates of 3'OMC are excreted extensively in bile. Circulating forms are mainly glucuronide conjugates of catechin and 3'OMC.<ref>{{cite journal |vauthors=Donovan JL, Crespy V, Manach C |title=Catechin is metabolized by both the small intestine and liver of rats |journal=J. Nutr. |volume=131 |issue=6 |pages=1753–7 |date=June 2001 |pmid=11385063 |url=http://jn.nutrition.org/cgi/pmidlookup?view=long&pmid=11385063|display-authors=etal}}</ref> Another study shows that catechin undergoes enzymatic oxidation by [[tyrosinase]] in the presence of [[glutathione]] (GSH) to form mono-, bi-, and tri-glutathione conjugates of catechin and mono- and bi-glutathione conjugates of a catechin dimer.<ref>{{cite journal |vauthors=Moridani MY, Scobie H, Salehi P, O'Brien PJ |title=Catechin metabolism: glutathione conjugate formation catalyzed by tyrosinase, peroxidase, and cytochrome p450 |journal=Chem. Res. Toxicol. |volume=14 |issue=7 |pages=841–8 |date=July 2001 |pmid=11453730 |doi=10.1021/tx000235o}}</ref>
Plasma catechin metabolites are present as conjugated forms and mainly constituted by [[glucuronic acid|glucuronidated]] derivatives. In the liver, the concentrations of catechin derivatives are lower than in plasma, and no accumulation is observed when the rats are adapted for 14 days to the supplemented diets. The hepatic metabolites are intensively methylated (90–95%), but in contrast to plasma, some free aglycones can be detected.<ref>{{cite journal | doi = 10.1016/S0891-5849(99)00159-8 | title = Comparison of the bioavailability of quercetin and catechin in rats | year = 1999 | last1 = Manach | first1 = Claudine | last2 = Texier | first2 = Odile | last3 = Morand | first3 = Christine | last4 = Crespy | first4 = Vanessa | last5 = Régérat | first5 = Françoise | last6 = Demigné | first6 = Christian | last7 = Rémésy | first7 = Christian | journal = Free Radical Biology and Medicine | volume = 27 | issue = 11–12 | pages = 1259–66 | pmid = 10641719}}</ref> Rats fed with (+)-catechin and (-)-epicatechin exhibit (+)-catechin 5-O-β-glucuronide and (-)-epicatechin 5-O-β-glucuronide in their body fluids.<ref>{{cite journal |vauthors=Harada M, Kan Y, Naoki H |title=Identification of the major antioxidative metabolites in biological fluids of the rat with ingested (+)-catechin and (-)-epicatechin |journal=Biosci. Biotechnol. Biochem. |volume=63 |issue=6 |pages=973–7 |date=June 1999 |pmid=10427682 |doi=10.1271/bbb.63.973|display-authors=etal}}</ref> The primary metabolite of (+)-catechin in rat plasma is a glucuronide in the nonmethylated form. In contrast, the primary metabolites of (-)-epicatechin in rat plasma are glucuronide and sulfoglucuronide in nonmethylated forms, and sulfate in the 3'-O-methylated forms (3'OMC).<ref>{{cite journal |vauthors=Baba S, Osakabe N, Natsume M, Muto Y, Takizawa T, Terao J |title=In vivo comparison of the bioavailability of (+)-catechin, (-)-epicatechin and their mixture in orally administered rats |journal=J. Nutr. |volume=131 |issue=11 |pages=2885–91 |date=November 2001 |pmid=11694613 |url=http://jn.nutrition.org/cgi/pmidlookup?view=long&pmid=11694613}}</ref> The recent use of radiocarbon-labeled epicatechin (<sup>14</sup>C<sub>2</sub>-(−)-epicatechin) demonstrated significant species-dependent differences in the metabolism of (-)-epicatechin in rat, mouse and human.<ref name="Ottaviani_2016">{{cite journal|last1=Ottaviani|first1=Javier|title=The metabolome of [2-14C] (−)-epicatechin in humans: implications for the assessment of efficacy, safety, and mechanisms of action of polyphenolic bioactives|journal=Nature-Scientific Reports|year=2016|volume=29034|issue=6|pages=29034|doi=10.1038/srep29034|pmc=4929566}}</ref> Catechin is absorbed into intestinal cells and metabolized extensively because no native catechin can be detected in plasma from the mesenteric vein.<ref name=lpi/> Additional methylation and sulfation occur in the liver, and glucuronide or sulfate conjugates of 3'OMC are excreted extensively in bile. Circulating forms are mainly glucuronide conjugates of catechin and 3'OMC.<ref>{{cite journal |vauthors=Donovan JL, Crespy V, Manach C |title=Catechin is metabolized by both the small intestine and liver of rats |journal=J. Nutr. |volume=131 |issue=6 |pages=1753–7 |date=June 2001 |pmid=11385063 |url=http://jn.nutrition.org/cgi/pmidlookup?view=long&pmid=11385063|display-authors=etal}}</ref> Another study shows that catechin undergoes enzymatic oxidation by [[tyrosinase]] in the presence of [[glutathione]] (GSH) to form mono-, bi-, and tri-glutathione conjugates of catechin and mono- and bi-glutathione conjugates of a catechin dimer.<ref>{{cite journal |vauthors=Moridani MY, Scobie H, Salehi P, O'Brien PJ |title=Catechin metabolism: glutathione conjugate formation catalyzed by tyrosinase, peroxidase, and cytochrome p450 |journal=Chem. Res. Toxicol. |volume=14 |issue=7 |pages=841–8 |date=July 2001 |pmid=11453730 |doi=10.1021/tx000235o}}</ref>


In the [[crab-eating macaque]] (''Macaca iris''), (+)-catechin administered orally or intraperitonally leads to the formation of 10 metabolites and notably to [[m-hydroxyphenylhydracrylic acid]] excreted in the urine.<ref>{{cite journal |author=Das NP |title=Studies on flavonoid metabolism. Excretion of m-hydroxyphenylhydracrylic acid from (plus)-catechin in the monkey (Macaca iris sp.) |journal=Drug Metab. Dispos. |volume=2 |issue=3 |pages=209–13 |year=1974 |pmid=4153081}}</ref>
In the [[crab-eating macaque]] (''Macaca iris''), (+)-catechin administered orally or intraperitonally leads to the formation of 10 metabolites and notably to [[m-hydroxyphenylhydracrylic acid]] excreted in the urine.<ref>{{cite journal |author=Das NP |title=Studies on flavonoid metabolism. Excretion of m-hydroxyphenylhydracrylic acid from (plus)-catechin in the monkey (Macaca iris sp.) |journal=Drug Metab. Dispos. |volume=2 |issue=3 |pages=209–13 |year=1974 |pmid=4153081}}</ref>
Line 242: Line 245:
==Bioactivity studies==
==Bioactivity studies==
{{refimprove section|date=January 2016}}
{{refimprove section|date=January 2016}}

===Vascular function===


Limited evidence from dietary studies indicates that catechins may have an effect on [[endothelium]]-dependent [[vasodilation]] which could contribute to normal [[blood flow]] regulation in humans.<ref name="pnas">{{cite journal|pmid=16418281|pmc=1327732|year=2006|author1=Schroeter|first1=H|title=(-)-Epicatechin mediates beneficial effects of flavanol-rich cocoa on vascular function in humans|journal=Proceedings of the National Academy of Sciences|volume=103|issue=4|pages=1024–9|last2=Heiss|first2=C|last3=Balzer|first3=J|last4=Kleinbongard|first4=P|last5=Keen|first5=C. L.|last6=Hollenberg|first6=N. K.|last7=Sies|first7=H|last8=Kwik-Uribe|first8=C|last9=Schmitz|first9=H. H.|last10=Kelm|first10=M|doi=10.1073/pnas.0510168103}}</ref><ref>{{cite journal|pmid=22301923|url=http://ajcn.nutrition.org/content/95/3/740.long|year=2012|author1=Hooper|first1=L|title=Effects of chocolate, cocoa, and flavan-3-ols on cardiovascular health: A systematic review and meta-analysis of randomized trials|journal=American Journal of Clinical Nutrition|volume=95|issue=3|pages=740–51|last2=Kay|first2=C|last3=Abdelhamid|first3=A|last4=Kroon|first4=P. A.|last5=Cohn|first5=J. S.|last6=Rimm|first6=E. B.|last7=Cassidy|first7=A|doi=10.3945/ajcn.111.023457}}</ref> Due to extensive metabolism during digestion, the fate and activity of catechin metabolites responsible for this effect are unknown.<ref name=lpi/><ref name=pnas/> The [[European Food Safety Authority]] established that cocoa flavanols have an effect on vascular function in healthy adults by concluding: "cocoa flavanols help maintain endothelium-dependent vasodilation, which contributes to normal blood flow".<ref>{{cite journal |last= EFSA Panel on Dietetic Products, Nutrition and Allergies (NDA) |date=2012 |title=Scientific opinion on the substantiation of a health claim related to cocoa flavanols and maintenance of normal endothelium-dependent vasodilation pursuant to Article 13(5) of Regulation (EC) No 1924/2006 |journal= EFSA Journal|publisher= Wiley|volume=10 |issue=7 |pages=2809 |doi= 10.2903/j.efsa.2012.2809|url=https://www.efsa.europa.eu/en/efsajournal/pub/2809|access-date=25 July 2016}}</ref>
Limited evidence from dietary studies indicates that catechins may have an effect on [[endothelium]]-dependent [[vasodilation]] which could contribute to normal [[blood flow]] regulation in humans.<ref name="pnas">{{cite journal|pmid=16418281|pmc=1327732|year=2006|author1=Schroeter|first1=H|title=(-)-Epicatechin mediates beneficial effects of flavanol-rich cocoa on vascular function in humans|journal=Proceedings of the National Academy of Sciences|volume=103|issue=4|pages=1024–9|last2=Heiss|first2=C|last3=Balzer|first3=J|last4=Kleinbongard|first4=P|last5=Keen|first5=C. L.|last6=Hollenberg|first6=N. K.|last7=Sies|first7=H|last8=Kwik-Uribe|first8=C|last9=Schmitz|first9=H. H.|last10=Kelm|first10=M|doi=10.1073/pnas.0510168103}}</ref><ref>{{cite journal|pmid=22301923|url=http://ajcn.nutrition.org/content/95/3/740.long|year=2012|author1=Hooper|first1=L|title=Effects of chocolate, cocoa, and flavan-3-ols on cardiovascular health: A systematic review and meta-analysis of randomized trials|journal=American Journal of Clinical Nutrition|volume=95|issue=3|pages=740–51|last2=Kay|first2=C|last3=Abdelhamid|first3=A|last4=Kroon|first4=P. A.|last5=Cohn|first5=J. S.|last6=Rimm|first6=E. B.|last7=Cassidy|first7=A|doi=10.3945/ajcn.111.023457}}</ref> Due to extensive metabolism during digestion, the fate and activity of catechin metabolites responsible for this effect are unknown.<ref name=lpi/><ref name=pnas/> The [[European Food Safety Authority]] established that cocoa flavanols have an effect on vascular function in healthy adults by concluding: "cocoa flavanols help maintain endothelium-dependent vasodilation, which contributes to normal blood flow".<ref>{{cite journal |last= EFSA Panel on Dietetic Products, Nutrition and Allergies (NDA) |date=2012 |title=Scientific opinion on the substantiation of a health claim related to cocoa flavanols and maintenance of normal endothelium-dependent vasodilation pursuant to Article 13(5) of Regulation (EC) No 1924/2006 |journal= EFSA Journal|publisher= Wiley|volume=10 |issue=7 |pages=2809 |doi= 10.2903/j.efsa.2012.2809|url=https://www.efsa.europa.eu/en/efsajournal/pub/2809|access-date=25 July 2016}}</ref>

===Immune function===
Catechin and its metabolites can bind tightly to red blood cells and thereby induce the development of [[autoantibodies|Autoantibody]], resulting in [[haemolytic anaemia]] and [[renal failure]]. <ref>{{cite book |author1=Martinez SE | author2=Davies NM|author3=Reynolds JK |date=2013 |title= Methods of Analysis, Preclinical and Clinical Pharmacokinetics, Safety, and Toxicology|chapter=Toxicology and Safety of Flavonoids|publisher=John Wiley & Son |page=257 |isbn= 978-0-470-57871-1}}


== Botanical effects ==
== Botanical effects ==

Revision as of 09:02, 26 July 2016

Catechin
Chemical structure of (+)-Catechin
Names
IUPAC name
(2R,3S)-2-(3,4-dihydroxyphenyl)-3,4-dihydro-2H-chromene-3,5,7-triol
Other names
Cianidanol
Cyanidanol
(+)-catechin
D-Catechin
Catechinic acid
Catechuic acid
Cianidol
Dexcyanidanol
(2R,3S)-Catechin
2,3-trans-catechin
3,3',4',5,7–flavanpentol
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.005.297 Edit this at Wikidata
UNII
  • InChI=1S/C15H14O6/c16-8-4-11(18)9-6-13(20)15(21-14(9)5-8)7-1-2-10(17)12(19)3-7/h1-5,13,15-20H,6H2/t13-,15+/m0/s1 checkY
    Key: PFTAWBLQPZVEMU-DZGCQCFKSA-N checkY
  • InChI=1/C15H14O6/c16-8-4-11(18)9-6-13(20)15(21-14(9)5-8)7-1-2-10(17)12(19)3-7/h1-5,13,15-20H,6H2/t13-,15+/m0/s1
    Key: PFTAWBLQPZVEMU-DZGCQCFKBX
  • Oc1ccc(cc1O)[C@H]3Oc2cc(O)cc(O)c2C[C@@H]3O
Properties
C15H14O6
Molar mass 290.271 g·mol−1
Appearance Colorless solid
Melting point 175 to 177 °C (347 to 351 °F; 448 to 450 K)
UV-vis (λmax) 276 nm
+14.0°
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Mutagenic for mammalian somatic cells, mutagenic for bacteria and yeast
Lethal dose or concentration (LD, LC):
(+)-catechin : 10,000 mg/kg in rat (RTECS)
10,000 mg/kg in mouse
3,890 mg/kg in rat (other source)
Safety data sheet (SDS) sciencelab AppliChem
Pharmacology
Oral
Pharmacokinetics:
Urines
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)

Catechin /ˈkæt[invalid input: 'ɨ']tʃɪn/ is a flavan-3-ol, a type of natural phenol and antioxidant. It is a plant secondary metabolite. It belongs to the group of flavan-3-ols (or simply flavanols), part of the chemical family of flavonoids.

The name of the catechin chemical family derives from catechu, which is the tannic juice or boiled extract of Mimosa catechu (Acacia catechu L.f)[1]

Chemistry

Catechin numbered

Catechin possesses two benzene rings (called the A- and B-rings) and a dihydropyran heterocycle (the C-ring) with a hydroxyl group on carbon 3. The A ring is similar to a resorcinol moiety while the B ring is similar to a catechol moiety. There are two chiral centers on the molecule on carbons 2 and 3. Therefore, it has four diastereoisomers. Two of the isomers are in trans configuration and are called catechin and the other two are in cis configuration and are called epicatechin.

The most common catechin isomer is the (+)-catechin. The other stereoisomer is (-)-catechin or ent-catechin. The most common epicatechin isomer is (-)-epicatechin (also known under the names L-epicatechin, epicatechol, (-)-epicatechol, l-acacatechin, l-epicatechol, epi-catechin, 2,3-cis-epicatechin or (2R,3R)-(-)-epicatechin).

The different epimers can be distinguished using chiral column chromatography.[2]

Making reference to no particular isomer, the molecule can just be called catechin. Mixtures of the different enantiomers can be called (+/-)-catechin or DL-catechin and (+/-)-epicatechin or DL-epicatechin.

  • Diastereoisomers gallery
  • (+)-catechin (2R,3S)
    (+)-catechin (2R,3S)
  • (-)-catechin (2S,3R)
    (-)-catechin (2S,3R)
  • (-)-epicatechin (2R,3R)
    (-)-epicatechin (2R,3R)
  • (+)-epicatechin (2S,3S)
    (+)-epicatechin (2S,3S)
3D view of "pseudoequatorial" (E) conformation of(+)-catechin

Moreover, the flexibility of the C-ring allows for two conformation isomers, putting the B ring either in a pseudoequatorial position (E conformer) or in a pseudoaxial position (A conformer). Studies confirmed that (+)-catechin adopts a mixture of A- and E-conformers in aqueous solution and their conformational equilibrium has been evaluated to be 33:67.[3]

Regarding the antioxidant activity, (+)-catechin has been found to be the most powerful scavenger between different members of the different classes of flavonoids. The ability to quench singlet oxygen seems to be in relation with the chemical structure of catechin, with the presence of the catechol moiety on ring B and the presence of a hydroxyl group activating the double bond on ring C.[4]

Catechin exists in the form of a glycoside.[5] Antioxidant properties can also be provided using a catechin associated with a sugar. In 1975-76, a group of USSR scientists of Kaz ssr discovered first the catechin rhamnoside using the plants of Filipendula that grow in that region. Pioneer and head of the discovery was PhD N. D. Storozhenko born in 1944. Though not thoroughly studied, the rhamnoside of catechin can enter the blood cell without breaking the outer layer.

Oxidation

Electrochemical experiments show that (+)-catechin oxidation mechanism proceeds in sequential steps, related with the catechol and resorcinol groups and the oxidation is pH-dependent. The oxidation of the catechol 3′,4′-dihydroxyl electron-donating groups occurs first, at very low positive potentials, and is a reversible reaction. The hydroxyl groups of the resorcinol moiety oxidised afterwards were shown to undergo an irreversible oxidation reaction.[6]

Spectral data

UV spectrum of catechin.
UV-Vis
Lambda-max: 276 nm
Extinction coefficient (log ε) 4.01
IR
Major absorption bands 1600 cm−1(benzene rings)
NMR
Proton NMR


(500 MHz, CD3OD):
Reference[7]
d : doublet, dd : doublet of doublets,
m : multiplet, s : singlet

δ :

2.49 (1H, dd, J = 16.0, 8.6 Hz, H-4a),
2.82 (1H, dd, J = 16.0, 1.6 Hz, H-4b),
3.97 (1H, m, H-3),
4.56 (1H, d, J = 7.8 Hz, H-2),
5.86 (1H, d, J = 2.1 Hz, H-6),
5.92 (1H, d, J = 2.1 Hz, H-8),
6.70 (1H, dd, J = 8.1, 1.8 Hz, H-6′),
6.75 (1H, d, J = 8.1 Hz, H-5′),
6.83 (1H, d, J = 1.8 Hz, H-2′)

Carbon-13 NMR
Other NMR data
MS
Masses of
main fragments 		ESI-MS [M+H]+ m/z : 291.0


273 water loss
139 Retro Diels Alder
123
165
147

Natural occurrences

(+)-Catechin and (-)-epicatechin as well as their gallic acid conjugates are ubiquitous constituents of vascular plants, and frequent components of traditional herbal remedies, such as the Chinese medicine plant Uncaria rhynchophylla and others. The two isomers are mostly associated with cacao and tea constituents.

(-)-Epicatechin can be found in cacao beans and was first called kakaool or cacao-ol.[8] It was isolated from green tea by Michiyo Tsujimura in 1929.[9] Maximilian Nierenstein was among those who proved the presence of catechin in cocoa beans in 1931.[10]

In food

Main articles: Phenolic content in tea and Phenolic content in wine

Catechins and epicatechins are found in cocoa,[11] which, according to one database, has the highest content (108 mg/100 g) of catechins among foods analyzed, followed by prune juice (25 mg/100 ml) and broad bean pod (16 mg/100 g).[12] Açaí oil, obtained from the fruit of the açaí palm (Euterpe oleracea), contains (+)-catechins (67 mg/kg).[13] (-)-Epicatechin and (+)-catechin are among the main natural phenols in argan oil.[14]

Catechins are diverse among foods,[12] from peaches[15] to green tea and vinegar.[12][16] Catechins are found in barley grain where they are the main phenolic compound responsible for dough discoloration.[17]

see also : List of phytochemicals in food, List of micronutrients and List of antioxidants in food

Taste

The taste associated with monomeric (+)-catechin or (-)-epicatechin is described as not exactly astringent, nor exactly bitter.[18]

Medicinal use

(+)-catechin has been used to treat acute viral hepatitis [19] and was marketed under the name Catergen by Zyma (now Novartis). Severe side effects (see Catechin#Immune function) lead to the withdrawal of the drug.

Metabolism

Biosynthesis

The biosynthesis of catechin begins with a 4-hydroxycinnamoyl CoA starter unit which undergoes chain extension by the addition of three malonyl-CoAs through a PKSIII pathway. 4-hydroxycinnamoyl CoA is biosynthesized from L-phenylalanine through the Shikimate pathway. L-phenylalanine is first deaminated by phenylalanine ammonia lyase (PAL) forming cinnamic acid which is then oxidized to 4-hydroxycinnamic acid by cinnamate 4-hydroyxylase. Chalcone synthase then catalyzes the condensation of 4-hydroxycinnamoyl CoA and three molecules of malonyl-CoA to form chalcone. Chalcone is then isomerized to naringenin by chalcone isomerase which is oxidized to eriodictyol by flavonoid 3’- hydroxylase and further oxidized to taxifolin by flavanone 3-hydroxylase. Taxifolin is then reduced by dihydroflavanol 4-reductase and leucoanthocyanidin reductase to yield catechin. The biosynthesis of catechin is shown below[20][21][22]

Leucocyanidin reductase (LCR) uses 2,3-trans-3,4-cis-leucocyanidin to produce (+)-catechin and is the first enzyme in the proanthocyanidins (PA)-specific pathway. Its activity has been measured in leaves, flowers, and seeds of the legumes Medicago sativa, Lotus japonicus, Lotus uliginosus, Hedysarum sulfurescens, and Robinia pseudoacacia.[23] The enzyme is also present in Vitis vinifera (grape).[24]

Biodegradation

Catechin oxygenase, a key enzyme in the degradation of catechin, is present in fungi and bacteria.[25]

Among bacteria, degradation of (+)-catechin can be achieved by Acinetobacter calcoaceticus. Catechin is metabolized to protocatechuic acid (PCA) and phloroglucinol carboxylic acid (PGCA).[26] It is also degraded by Bradyrhizobium japonicum. Phloroglucinol carboxylic acid is further decarboxylated to phloroglucinol, which is dehydroxylated to resorcinol. Resorcinol is hydroxylated to hydroxyquinol. Protocatechuic acid and hydroxyquinol undergo intradiol cleavage through protocatechuate 3,4-dioxygenase and hydroxyquinol 1,2-dioxygenase to form β-carboxy cis, cis-muconic acid and maleyl acetate.[27]

Among fungi, degradation of catechin can be achieved by Chaetomium cupreum.[28]

Humans

Human metabolites of epicatechin (excluding colonic metabolites)[29]

Catechins are metabolised in the gastrointestinal tract[30] and in the liver, resulting in so-called structurally-related epicatechin metabolites (SREM) that interact with the colonic microbiome.[31] The main metabolic pathways for SREMs are glucuronidation, sulphation and methylation of the catechol group by catechol-O-methyl transferase, with only small amounts detected in plasma.[32]

The majority of epicatechins are metabolized to gamma-valerolactones and hippuric acids which undergo biotransformation, glucuronidation, sulphation and methylation in the liver.[31]

Research

Plasma catechin metabolites are present as conjugated forms and mainly constituted by glucuronidated derivatives. In the liver, the concentrations of catechin derivatives are lower than in plasma, and no accumulation is observed when the rats are adapted for 14 days to the supplemented diets. The hepatic metabolites are intensively methylated (90–95%), but in contrast to plasma, some free aglycones can be detected.[33] Rats fed with (+)-catechin and (-)-epicatechin exhibit (+)-catechin 5-O-β-glucuronide and (-)-epicatechin 5-O-β-glucuronide in their body fluids.[34] The primary metabolite of (+)-catechin in rat plasma is a glucuronide in the nonmethylated form. In contrast, the primary metabolites of (-)-epicatechin in rat plasma are glucuronide and sulfoglucuronide in nonmethylated forms, and sulfate in the 3'-O-methylated forms (3'OMC).[35] The recent use of radiocarbon-labeled epicatechin (14C2-(−)-epicatechin) demonstrated significant species-dependent differences in the metabolism of (-)-epicatechin in rat, mouse and human.[29] Catechin is absorbed into intestinal cells and metabolized extensively because no native catechin can be detected in plasma from the mesenteric vein.[31] Additional methylation and sulfation occur in the liver, and glucuronide or sulfate conjugates of 3'OMC are excreted extensively in bile. Circulating forms are mainly glucuronide conjugates of catechin and 3'OMC.[36] Another study shows that catechin undergoes enzymatic oxidation by tyrosinase in the presence of glutathione (GSH) to form mono-, bi-, and tri-glutathione conjugates of catechin and mono- and bi-glutathione conjugates of a catechin dimer.[37]

In the crab-eating macaque (Macaca iris), (+)-catechin administered orally or intraperitonally leads to the formation of 10 metabolites and notably to m-hydroxyphenylhydracrylic acid excreted in the urine.[38]

Biotransformation

Biotransformation of (+)-catechin into taxifolin by a two-step oxidation can be achieved by Burkholderia sp.[39]

The laccase/ABTS system oxidizes (+)-catechin to oligomeric products[40] of which proanthocyanidin A2 is a dimer.

(+)-Catechin and (-)-epicatechin are transformed by the endophytic filamentous fungus Diaporthe sp. into the 3,4-cis-dihydroxyflavan derivatives, (+)-(2R,3S,4S)-3,4,5,7,3',4'-hexahydroxyflavan (leucocyanidin) and (-)-(2R,3R,4R)-3,4,5,7,3',4'-hexahydroxyflavan, respectively, whereas (-)-catechin and (+)-epicatechin with a 2S-phenyl group resisted the biooxidation.[41]

Leucoanthocyanidin reductase (LAR) uses (2R,3S)-catechin, NADP+ and H2O to produce 2,3-trans-3,4-cis-leucocyanidin, NADPH, and H+. Its gene expression has been studied in developing grape berries and grapevine leaves.[42]

Catechin and epicatechin are the building blocks of the proanthocyanidins, a type of condensed tannin.

Glycosides

Bioactivity studies

Vascular function

Limited evidence from dietary studies indicates that catechins may have an effect on endothelium-dependent vasodilation which could contribute to normal blood flow regulation in humans.[45][46] Due to extensive metabolism during digestion, the fate and activity of catechin metabolites responsible for this effect are unknown.[31][45] The European Food Safety Authority established that cocoa flavanols have an effect on vascular function in healthy adults by concluding: "cocoa flavanols help maintain endothelium-dependent vasodilation, which contributes to normal blood flow".[47]

Immune function

Catechin and its metabolites can bind tightly to red blood cells and thereby induce the development of Autoantibody, resulting in haemolytic anaemia and renal failure. Cite error: A <ref> tag is missing the closing </ref> (see the help page). Centaurea maculosa, the spotted knapweed often studied for this behavior, releases catechin isomers into the ground through its roots, potentially having effects as an antibiotic or herbicide. One hypothesis is that it causes a reactive oxygen species wave through the target plant's root to kill root cells by apoptosis.[48] Most plants in the European ecosystem have defenses against catechin, but few plants are protected against it in the North American ecosystem where Centaurea maculosa is an invasive, uncontrolled weed.[49]

Catechin acts as an infection-inhibiting factor in strawberry leaves.[50] Epicatechin and catechin may prevent coffee berry disease by inhibiting appressorial melanization of Colletotrichum kahawae.[51]

References

  1. ^ Zheng LT, Ryu GM, Kwon BM, Lee WH, Suk K (June 2008). "Anti-inflammatory effects of catechols in lipopolysaccharide-stimulated microglia cells: inhibition of microglial neurotoxicity". Eur. J. Pharmacol. 588 (1): 106–13. doi:10.1016/j.ejphar.2008.04.035. PMID 18499097.
  2. ^ Rinaldo D, Batista JM, Rodrigues J, et al. (August 2010). "Determination of catechin diastereomers from the leaves of Byrsonima species using chiral HPLC-PAD-CD". Chirality. 22 (8): 726–33. doi:10.1002/chir.20824. PMID 20143413.
  3. ^ Kríz Z, Koca J, Imberty A, Charlot A, Auzély-Velty R (July 2003). "Investigation of the complexation of (+)-catechin by β-cyclodextrin by a combination of NMR, microcalorimetry and molecular modeling techniques". Org. Biomol. Chem. 1 (14): 2590–5. doi:10.1039/B302935M. PMID 12956082.
  4. ^ Tournaire C, Croux S, Maurette MT, et al. (August 1993). "Antioxidant activity of flavonoids: Efficiency of singlet oxygen (1Δg) quenching". J. Photochem. Photobiol. B, Biol. 19 (3): 205–15. doi:10.1016/1011-1344(93)87086-3. PMID 8229463.
  5. ^ Chumbalov, T. K.; Pashinina, L. T.; Storozhenko, N. D. (1976). "Catechin 7-rhamnoside fromSpiraea hypericifolia". Chemistry of Natural Compounds. 12 (2): 232–233. doi:10.1007/BF00566356.
  6. ^ Janeiro, Patricia; Oliveira Brett, Ana Maria (2004). "Catechin electrochemical oxidation mechanisms". Analytica Chimica Acta. 518: 109–115. doi:10.1016/j.aca.2004.05.038.
  7. ^ Lin, Yi-Pei; Chen, Tai-Yuan; Tseng, Hsiang-Wen; Lee, Mei-Hsien; Chen, Shui-Tein (2009). "Neural cell protective compounds isolated from Phoenix hanceana var. Formosana". Phytochemistry. 70 (9): 1173–81. doi:10.1016/j.phytochem.2009.06.006. PMID 19628235.
  8. ^ Freudenberg, Karl; Cox, Richard F. B.; Braun, Emil (1932). "The Catechin of the Cacao Bean1". Journal of the American Chemical Society. 54 (5): 1913–1917. doi:10.1021/ja01344a026.
  9. ^ "Michiyo Tsujimura (1888–1969)". Ochanomizu University. Retrieved 10 November 2015.
  10. ^ Adam, W. B.; Hardy, F.; Nierenstein, M. (1931). "The Catechin of the Cacao Bean". Journal of the American Chemical Society. 53 (2): 727–728. doi:10.1021/ja01353a041.
  11. ^ Kwik-Uribe C, Bektash RM (2008). "Cocoa flavanols - measurement, bioavailability and bioactivity" (PDF). Asia Pac J Clin Nutr. 17 (Suppl 1): 280–3. PMID 18296356.
  12. ^ a b c "Polyphenols in green tea infusion". Phenol-Explorer, v 3.5. 2014. Retrieved 1 November 2014.
  13. ^ Pacheco-Palencia LA, Mertens-Talcott S, Talcott ST (June 2008). "Chemical composition, antioxidant properties, and thermal stability of a phytochemical enriched oil from Acai (Euterpe oleracea Mart.)". J. Agric. Food Chem. 56 (12): 4631–6. doi:10.1021/jf800161u. PMID 18522407.
  14. ^ ., Z. Charrouf; ., D. Guillaume (2007). "Phenols and Polyphenols from Argania spinosa". American Journal of Food Technology. 2 (7): 679–683. doi:10.3923/ajft.2007.679.683. {{cite journal}}: |last1= has numeric name (help)
  15. ^ Cheng, Guiwen W.; Crisosto, Carlos H. (1995). "Browning Potential, Phenolic Composition, and Polyphenoloxidase Activity of Buffer Extracts of Peach and Nectarine Skin Tissue" (PDF). J. Amer. Soc. Hort. Sci. 120 (5): 835–838.
  16. ^ Gálvez, Miguel Carrero; Barroso, Carmelo García; Pérez-Bustamante, Juan Antonio (1994). "Analysis of polyphenolic compounds of different vinegar samples". Zeitschrift für Lebensmittel-Untersuchung und -Forschung. 199 (1): 29–31. doi:10.1007/BF01192948.
  17. ^ Quinde-Axtell, Zory; Baik, Byung-Kee (2006). "Phenolic Compounds of Barley Grain and Their Implication in Food Product Discoloration". J. Agric. Food Chem. 54 (26): 9978–9984. doi:10.1021/jf060974w. PMID 17177530.
  18. ^ Kielhorn, S; Thorngate Iii, J.H (1999). "Oral sensations associated with the flavan-3-ols (+)-catechin and (−)-epicatechin". Food Quality and Preference. 10 (2): 109–116. doi:10.1016/S0950-3293(98)00049-4.
  19. ^ Bode, JC (1987). Assessment and Management of Hepatobiliary Disease. Berlin: Springer-Verlag. p. 371. doi:10.1007/978-3-642-72631-6. ISBN 978-3-642-72631-6.
  20. ^ Rani, Arti; Singh, Kashmir; Ahuja, Paramvir S.; Kumar, Sanjay (2012). "Molecular regulation of catechins biosynthesis in tea \Camellia sinensis (L.) O. Kuntze]". Gene. 495 (2): 205–10. doi:10.1016/j.gene.2011.12.029. PMID 22226811.
  21. ^ Punyasiri, P.A.N.; Abeysinghe, I.S.B.; Kumar, V.; Treutter, D.; Duy, D.; Gosch, C.; Martens, S.; Forkmann, G.; Fischer, T.C. (2004). "Flavonoid biosynthesis in the tea plant Camellia sinensis: Properties of enzymes of the prominent epicatechin and catechin pathways". Archives of Biochemistry and Biophysics. 431 (1): 22–30. doi:10.1016/j.abb.2004.08.003. PMID 15464723.
  22. ^ Dewick, Paul M. (2009). Medicinal Natural Products: A Biosynthetic Approach (3rd ed.). UK: John Wiley & Sons. ISBN 978-0-470-74167-2.[page needed]
  23. ^ Skadhauge, Birgitte; Gruber, Margaret Y.; Thomsen, Karl Kristian; Von Wettstein, Diter (April 1997). "Leucocyanidin Reductase Activity and Accumulation of Proanthocyanidins in Developing Legume Tissues". American Journal of Botany. 84 (4): 494–503. doi:10.2307/2446026. JSTOR 2446026.
  24. ^ Maugé C, Granier T, d'Estaintot BL, et al. (April 2010). "Crystal structure and catalytic mechanism of leucoanthocyanidin reductase from Vitis vinifera". J. Mol. Biol. 397 (4): 1079–91. doi:10.1016/j.jmb.2010.02.002. PMID 20138891.
  25. ^ Biodegradation of Catechin. M Arunachalam, M Mohan Raj, N Mohan and A Mahadevan, Proc. Indian natn Sci Acad. B69 No. 4 pp 353-370 (2003)
  26. ^ Arunachalam, M; Mohan, N; Sugadev, R; Chellappan, P; Mahadevan, A (2003). "Degradation of (+)-catechin by Acinetobacter calcoaceticus MTC 127". Biochimica et Biophysica Acta (BBA) - General Subjects. 1621 (3): 261–265. doi:10.1016/S0304-4165(03)00077-1.
  27. ^ Hopper, Waheeta; Mahadevan, A. (1997). "Degradation of catechin by Bradyrhizobium japonicum". Biodegradation. 8 (3): 159–165. doi:10.1023/A:1008254812074.
  28. ^ Sambandam, T.; Mahadevan, A. (1993). "Degradation of catechin and purification and partial characterization of catechin oxygenase fromChaetomium cupreum". World Journal of Microbiology & Biotechnology. 9: 37–44. doi:10.1007/BF00656513.
  29. ^ a b Ottaviani, Javier (2016). "The metabolome of [2-14C] (−)-epicatechin in humans: implications for the assessment of efficacy, safety, and mechanisms of action of polyphenolic bioactives". Nature-Scientific Reports. 29034 (6): 29034. doi:10.1038/srep29034. PMC 4929566.
  30. ^ Actis-Goretta, L; Lévèques, A; Rein, M; Teml, A; Schäfer, C; Hofmann, U; Li, H; Schwab, M; Eichelbaum, M; Williamson, G (2013). "Intestinal absorption, metabolism, and excretion of (-)-epicatechin in healthy humans assessed by using an intestinal perfusion technique". American Journal of Clinical Nutrition. 98 (4): 924–33. doi:10.3945/ajcn.113.065789. PMID 23864538.
  31. ^ a b c d "Flavonoids". Linus Pauling Institute, Oregon State University, Corvallis. 2016. Retrieved 24 July 2016.
  32. ^ Ottaviani, J. I.; Momma, T. Y.; Kuhnle, G. K.; Keen, C. L.; Schroeter, H (2012). "Structurally related (-)-epicatechin metabolites in humans: Assessment using de novo chemically synthesized authentic standards". Free Radical Biology and Medicine. 52 (8): 1403–12. doi:10.1016/j.freeradbiomed.2011.12.010. PMID 22240152.
  33. ^ Manach, Claudine; Texier, Odile; Morand, Christine; Crespy, Vanessa; Régérat, Françoise; Demigné, Christian; Rémésy, Christian (1999). "Comparison of the bioavailability of quercetin and catechin in rats". Free Radical Biology and Medicine. 27 (11–12): 1259–66. doi:10.1016/S0891-5849(99)00159-8. PMID 10641719.
  34. ^ Harada M, Kan Y, Naoki H, et al. (June 1999). "Identification of the major antioxidative metabolites in biological fluids of the rat with ingested (+)-catechin and (-)-epicatechin". Biosci. Biotechnol. Biochem. 63 (6): 973–7. doi:10.1271/bbb.63.973. PMID 10427682.
  35. ^ Baba S, Osakabe N, Natsume M, Muto Y, Takizawa T, Terao J (November 2001). "In vivo comparison of the bioavailability of (+)-catechin, (-)-epicatechin and their mixture in orally administered rats". J. Nutr. 131 (11): 2885–91. PMID 11694613.
  36. ^ Donovan JL, Crespy V, Manach C, et al. (June 2001). "Catechin is metabolized by both the small intestine and liver of rats". J. Nutr. 131 (6): 1753–7. PMID 11385063.
  37. ^ Moridani MY, Scobie H, Salehi P, O'Brien PJ (July 2001). "Catechin metabolism: glutathione conjugate formation catalyzed by tyrosinase, peroxidase, and cytochrome p450". Chem. Res. Toxicol. 14 (7): 841–8. doi:10.1021/tx000235o. PMID 11453730.
  38. ^ Das NP (1974). "Studies on flavonoid metabolism. Excretion of m-hydroxyphenylhydracrylic acid from (plus)-catechin in the monkey (Macaca iris sp.)". Drug Metab. Dispos. 2 (3): 209–13. PMID 4153081.
  39. ^ Matsuda M, Otsuka Y, Jin S, et al. (February 2008). "Biotransformation of (+)-catechin into taxifolin by a two-step oxidation: primary stage of (+)-catechin metabolism by a novel (+)-catechin-degrading bacteria, Burkholderia sp. KTC-1, isolated from tropical peat". Biochem. Biophys. Res. Commun. 366 (2): 414–9. doi:10.1016/j.bbrc.2007.11.157. PMID 18068670.
  40. ^ Osman, A.M.; Wong, K.K.Y.; Fernyhough, A. (2007). "The laccase/ABTS system oxidizes (+)-catechin to oligomeric products". Enzyme and Microbial Technology. 40 (5): 1272–1279. doi:10.1016/j.enzmictec.2006.09.018.
  41. ^ Shibuya H, Agusta A, Ohashi K, Maehara S, Simanjuntak P (July 2005). "Biooxidation of (+)-catechin and (-)-epicatechin into 3,4-dihydroxyflavan derivatives by the endophytic fungus Diaporthe sp. isolated from a tea plant". Chem. Pharm. Bull. 53 (7): 866–7. doi:10.1248/cpb.53.866. PMID 15997157.
  42. ^ Bogs J, Downey MO, Harvey JS, Ashton AR, Tanner GJ, Robinson SP (October 2005). "Proanthocyanidin synthesis and expression of genes encoding leucoanthocyanidin reductase and anthocyanidin reductase in developing grape berries and grapevine leaves". Plant Physiol. 139 (2): 652–63. doi:10.1104/pp.105.064238. JSTOR 4281902. PMC 1255985. PMID 16169968.
  43. ^ Friedrich, Wolfgang; Galensa, Rudolf (2002). "Identification of a new flavanol glucoside from barley ( Hordeum vulgare L.) and malt". European Food Research and Technology. 214 (5): 388–393. doi:10.1007/s00217-002-0498-x.
  44. ^ Jin QD, Mu QZ (1991). "[Study on glycosidal constituents from Epigynum auritum]". Yao Xue Xue Bao (in Chinese). 26 (11): 841–5. PMID 1823978.
  45. ^ a b Schroeter, H; Heiss, C; Balzer, J; Kleinbongard, P; Keen, C. L.; Hollenberg, N. K.; Sies, H; Kwik-Uribe, C; Schmitz, H. H.; Kelm, M (2006). "(-)-Epicatechin mediates beneficial effects of flavanol-rich cocoa on vascular function in humans". Proceedings of the National Academy of Sciences. 103 (4): 1024–9. doi:10.1073/pnas.0510168103. PMC 1327732. PMID 16418281.
  46. ^ Hooper, L; Kay, C; Abdelhamid, A; Kroon, P. A.; Cohn, J. S.; Rimm, E. B.; Cassidy, A (2012). "Effects of chocolate, cocoa, and flavan-3-ols on cardiovascular health: A systematic review and meta-analysis of randomized trials". American Journal of Clinical Nutrition. 95 (3): 740–51. doi:10.3945/ajcn.111.023457. PMID 22301923.
  47. ^ EFSA Panel on Dietetic Products, Nutrition and Allergies (NDA) (2012). "Scientific opinion on the substantiation of a health claim related to cocoa flavanols and maintenance of normal endothelium-dependent vasodilation pursuant to Article 13(5) of Regulation (EC) No 1924/2006". EFSA Journal. 10 (7). Wiley: 2809. doi:10.2903/j.efsa.2012.2809. Retrieved 25 July 2016.
  48. ^ Bais HP, Vepachedu R, Gilroy S, Callaway RM, Vivanco JM (September 2003). "Allelopathy and exotic plant invasion: from molecules and genes to species interactions". Science. 301 (5638): 1377–80. doi:10.1126/science.1083245. PMID 12958360.
  49. ^ Cite error: The named reference broz was invoked but never defined (see the help page).
  50. ^ Yamamoto M, Nakatsuka S, Otani H, Kohmoto K, Nishimura S (June 2000). "(+)-catechin acts as an infection-inhibiting factor in strawberry leaf". Phytopathology. 90 (6): 595–600. doi:10.1094/PHYTO.2000.90.6.595. PMID 18944538.
  51. ^ Chen Z, Liang J, Zhang C, Rodrigues CJ (October 2006). "Epicatechin and catechin may prevent coffee berry disease by inhibition of appressorial melanization of Colletotrichum kahawae". Biotechnol. Lett. 28 (20): 1637–40. doi:10.1007/s10529-006-9135-2. PMID 16955359.

External links

Look up Catechin or catechine in Wiktionary, the free dictionary.
Retrieved from "https://en.wikipedia.org/w/index.php?title=Catechin&oldid=731588795"