Caffeine, Xanthines, &c
Dr. Duke's Phytochemical and Ethnobotanical Databases:
Plants containing Caffeine and Theobromine:
Caffeine Theobromine
Camellia sinensis (leaf) - Tea 93,000 ppm 1,100 ppm
Paullinia cupana (seed) - Guarana 76,000 ppm 330 ppm
Coffea arabica (seed) - Coffee 32,000 ppm 18 ppm
Paullinia yoko (bark) - Yoko 27,300 ppm
Cola acuminata (seed) - Cola 25,000 ppm 1,000 ppm
Ilex paraguariensis (leaf) - Yerba Mate 20,000 ppm 5,000 ppm
Theobroma cacao (seed) - Cacao 12,900 ppm 33,500 ppm
Genipa americana (seed ) - Genipap 0- 22,500 ppm
Ilex vomitoria (leaf) - Yaupon Holly 3,000 - 9,000 ppm 500 - 3,000 ppm
Ilex cassine (leaf) - Dahoon Holly 500 - 2,000 ppm 1,000 - 7,000 ppm
http://carpe.umd.edu/Documents/2001/report-tachieobeng_brown2001.pdf (cola)
http://en.wikipedia.org/wiki/Yerba_mate
http://www.henriettesherbal.com/eclectic/kings/theobroma.html
http://en.wikipedia.org/wiki/Cocoa_bean
http://en.wikipedia.org/wiki/Genipa_americana
http://en.wikipedia.org/wiki/Guarana
Some other plants with low concentrations of Caffeine followed and were snipped.
Plants with significant Theobromine levels were added to the caffeine list.
Yaupon and Dahoon figures are derived from data in this report (methodology
differences probably exist):
Diversity of Methylxanthine Content in Ilex cassine L. and Ilex vomitoria Ait.:
Assessing Sources of the North American Stimulant Cassina
Adam L. Edwards and Bradley C. Bennett in Economic Botany 59(3):275-285. 2005
http://www.bioone.org/doi/abs/10.1663/0013-0001(2005)059%5B0275:DOMCII%5D2.0.CO%3B2
DUKE1992A: Duke, James A. 1992. Handbook of phytochemical constituents of GRAS herbs and other economic plants. Boca Raton, FL. CRC Press.
_______________________________________________
The Encyclopedia of psychoactive plants
Ratsch, Christian, Rochester, VT, Park St. Press 2005, 1st US ed.
Entries for: Ilex cassine Walter, Ilex guayusa Loesener, Ilex paraguariensis Saint-Hilaire, and Ilex vomitoria [Solander in] Aiton, and for Caffeine.
For Yaupon, this source says there are two botanically accepted subspecies and one form:
Ilex vomitoria Ait. ssp. vomitoria
Ilex vomitoria Ait. ssp. chiapensis (Sharp) E. Murr.
Ilex vomitoria Ait. f. pendula Foret et Solymosy
Also identifies two more varities:
Ilex vomitoria [Soland. in] Aiton var. chiapensis A.J. Sharp
Ilex vomitoria [Soland. in] Aiton var. yawkeyii Tarbox
Under Caffeine, the encyclopedia lists all the currently known plants containing caffeine:
Aquifoliacea: Ilex ambigua (Carolina Holly, Sand Holly) http://en.wikipedia.org/wiki/Ilex_ambigua
Ilex cassine, Ilex guayusa, Ilex paraguariensis, Ilex vomitoria, Ilex spp.
Cactaceae: Cereus jamacaru, Harrisia adscendens, Leocereus bahiensis, Pilocereus gounelli
Combretaceae: Combretum spp. http://en.wikipedia.org/wiki/Combretum
Nyctaginaceae: Neea theifera http://en.wikipedia.org/wiki/Nyctaginaceae
Rubiaceae: Coffea arabica, Coffea canephora, Coffea liberica, Coffea spp.
Sapindaceae: Paullinia cupana, Paullinia yoco, Paullinia spp.
Sterculiaceae: Brachychiton diversifolius http://en.wikipedia.org/wiki/Brachychiton, Cola acuminata, Cola nitida, Cola spp., Firmiana simplex http://en.wikipedia.org/wiki/Firmiana_simplex, Theobroma cacao, Theobroma spp.
Theaceae: Camellia sinensis
Turneraceae: Turnera diffusa (Damiana) http://en.wikipedia.org/wiki/Turnera_diffusa , Turnera ulmifolia (Yellow Alder)
----------------------------------------------------------------
Literature on Caffeine (Books)
The World of Caffeine - The Science and Culture of the World's Most Popular Drug
Bennett Alan Weinberg, and Bonnie K. Bealer. Routledge, NY and London 2001
Coffee, Tea, Chocolate, and the Brain ed. Astrid Nehlig CRC Press 2004
Caffeine and Behaviour - Current Views and Research Trends
B.S. Gupta, Ph.D. and Uma Gupta, Ph.D. CRC Press 1999
Caffeine and Health Jack E. James, PhD. Academic Press 1999
Caffeine ed. Gene A. Spiller, Ph.D., D.Sc., FACN CRC Press 1998
Chap. 10 - Basic Metabolism and Physiological Effects of the Methylxanthines.
Caffeine, Coffee, and Health ed. Silvio Garattini, M.D. Raven Press 1993
Caffeine - Perspectives from Recent Research ed. P.B. Dews Springer-Verlag 1984
Alcohol and Caffeine - A Study of Their Psychological Effects Harvey Nash, Ph.D. Thomas Books 1962
--------------------------------------------------------------------------------------------------------
http://en.wikipedia.org/wiki/Caffeine
EDinformatics: Education for the Information Age
Math and Science: Science of Cooking: Caffeine
http://www.edinformatics.com/math_science/science_of_cooking/caffeine.htm
Royal Society of Chemistry: Chemistry World, May 2011
Chemistry in Every Cup
http://www.rsc.org/chemistryworld/Issues/2011/May/ChemistryInEveryCup.asp
JIMSEVEN: JAMES HOFFMANN'S BLOG
Maillard Reaction, Strecker Degredation and Caramelisation. June 20th, 2006
http://www.jimseven.com/2006/06/20/maillard-reaction-strecker-degredation-and-caramelisation/
Formation of strecker aldehydes from polyphenol-derived quinones and alpha-amino
acids in a nonenzymic model system.
Rizzi GP. Procter & Gamble Company, Winton Hill Business Center, 6300 Center Hill
Road, Cincinnati, Ohio 45224, USA. [email protected]
J Agric Food Chem. 2006 Mar 8;54(5):1893-7.
Fruits and vegetables contain naturally occurring polyphenolic compounds that can undergo enzyme-catalyzed oxidation during food preparation. Many of these compounds contain catechol (1,2-dihydroxybenzene) moieties that may be transformed into o-quinone derivatives by polyphenoloxidases and molecular oxygen. Secondary reactions of the o-quinones include the Strecker degradation of ambient amino acids to form flavor-important volatile aldehydes. The purpose of this work was to investigate the mechanism of the polyphenol/o-quinone/Strecker degradation sequence in a nonenzymic model system. By using ferricyanide ion as the oxidant in pH 7.17 phosphate buffer at 22 degrees C, caffeic acid, chlorogenic acid, (+) catechin, and (-) epicatechin were caused to react with methionine and phenylalanine to produce Strecker aldehydes methional and phenylacetaldehyde in 0.032-0.42% molar yields (0.7-10 ppm in reaction mixtures). Also, by employing l-proline methyl ester in a reaction with 4-methylcatechol, a key reaction intermediate, 4-(2'-carbomethoxy-1'-pyrrolidinyl)-5-methyl-1,2-benzoquinone (7), was isolated and tentatively identified.
http://www.ncbi.nlm.nih.gov/pubmed/16506850
Caffeine in Yaupon was first reported in 1919.
Journal of the American Chemical Society
http://pubs.acs.org/doi/abs/10.1021/ja02229a019
http://en.wikipedia.org/wiki/Caffeine
EDinformatics: Education for the Information Age
Math and Science: Science of Cooking: Caffeine
http://www.edinformatics.com/math_science/science_of_cooking/caffeine.htm
Royal Society of Chemistry: Chemistry World, May 2011
Chemistry in Every Cup
http://www.rsc.org/chemistryworld/Issues/2011/May/ChemistryInEveryCup.asp
JIMSEVEN: JAMES HOFFMANN'S BLOG
Maillard Reaction, Strecker Degredation and Caramelisation. June 20th, 2006
http://www.jimseven.com/2006/06/20/maillard-reaction-strecker-degredation-and-caramelisation/
Formation of strecker aldehydes from polyphenol-derived quinones and alpha-amino
acids in a nonenzymic model system.
Rizzi GP. Procter & Gamble Company, Winton Hill Business Center, 6300 Center Hill
Road, Cincinnati, Ohio 45224, USA. [email protected]
J Agric Food Chem. 2006 Mar 8;54(5):1893-7.
Fruits and vegetables contain naturally occurring polyphenolic compounds that can undergo enzyme-catalyzed oxidation during food preparation. Many of these compounds contain catechol (1,2-dihydroxybenzene) moieties that may be transformed into o-quinone derivatives by polyphenoloxidases and molecular oxygen. Secondary reactions of the o-quinones include the Strecker degradation of ambient amino acids to form flavor-important volatile aldehydes. The purpose of this work was to investigate the mechanism of the polyphenol/o-quinone/Strecker degradation sequence in a nonenzymic model system. By using ferricyanide ion as the oxidant in pH 7.17 phosphate buffer at 22 degrees C, caffeic acid, chlorogenic acid, (+) catechin, and (-) epicatechin were caused to react with methionine and phenylalanine to produce Strecker aldehydes methional and phenylacetaldehyde in 0.032-0.42% molar yields (0.7-10 ppm in reaction mixtures). Also, by employing l-proline methyl ester in a reaction with 4-methylcatechol, a key reaction intermediate, 4-(2'-carbomethoxy-1'-pyrrolidinyl)-5-methyl-1,2-benzoquinone (7), was isolated and tentatively identified.
http://www.ncbi.nlm.nih.gov/pubmed/16506850
Caffeine in Yaupon was first reported in 1919.
Journal of the American Chemical Society
http://pubs.acs.org/doi/abs/10.1021/ja02229a019
--------------------------------------------------------------------
http://www.econbot.org/_about_/06_awards/awards_morton/pdfs/a_edwards.pdf
Poster by Adam Edwards (2006?)
Department of Biological Sciences,
Florida International University, Miami, FL
Edwards used HPLC and LC-MS to identify and quantify Caffeine, Theobromine, and Theophylline.
Fresh Yaupon was tinctured in a water-methanol solvent, and chloroform extractions were made from that solution to analyze.
http://en.wikipedia.org/wiki/Caffeine
http://en.wikipedia.org/wiki/Theobromine
http://en.wikipedia.org/wiki/Theophylline
These are the methylated Xanthines: Caffeine, Theobromine, and Theophylline
http://en.wikipedia.org/wiki/Xanthine
------------------------------------------------------
Diversity of Methylxanthine Content in Ilex cassine L. and Ilex vomitoria Ait.:
Assessing Sources of the North American Stimulant Cassina
Adam L. Edwards and Bradley C. Bennett
Center for Ethnobiology and Natural Products,
Department of Biological Sciences, Florida International University, Miami
Economic Botany 59(3):275-285. 2005
doi: 10.1663/0013-0001(2005)059[0275:DOMCII]2.0.CO;2
http://www.bioone.org/doi/abs/10.1663/0013-0001(2005)059%5B0275:DOMCII%5D2.0.CO%3B2
abstract, references, figures, and tables - not full text
includes a table of historical european names for Yaupon and Dahoon
Dahoon (Ilex cassine L.) has more theobromine and less caffeine than Yaupon.
-----------------------------------------------------------------------------------------------------------------------------
Dr. Putz reports in the Gainesville Sun that Yaupon is rich in antioxidants.
http://www.gainesville.com/article/20100408/NEWS/100409426
"UF researchers found that yaupon leaves have the anti-oxidation potential of blueberries. The leaves are chock full of various isomers of chlorogenic acid, coumaric acid, and a cocktail of flavonoids. Concentrations of these compounds, as well as the psychoactives caffeine and theobromine, are especially high in leaves from nitrogen-fertilized females. "
http://en.wikipedia.org/wiki/Flavonoid
http://en.wikipedia.org/wiki/Chlorogenic_acid
---------------------------------------------------------------------------------------------------
Oecologia. 2007 Feb;151(1):1-9. Epub 2006 Oct 18.
Nitrogen fertilizer and gender effects on the secondary metabolism of yaupon, a caffeine-containing North American holly.
Palumbo MJ, Putz FE, Talcott ST.
Department of Botany, University of Florida, Gainesville, FL
http://www.springerlink.com/content/kn682u522p5nj26g/
identifies cinnamic acid derivatives...
http://en.wikipedia.org/wiki/Cinnamic_acid
http://en.wikipedia.org/wiki/Coumaric_acid
Briefly, Palumbo shows that Yaupon plants that receive extra nitrogen exhibit increases in foliar concentrations of caffeine, but not phenolic and other compounds. Further they show that female Yaupon plants have larger increases of caffeine concentrations than male plants in response to fertilization. Also examines antioxidant potentials of Yaupon plants.
--------------------------------------------------------------------------------------------------------------------------------
YERBA MATE, Ilex paraguariensis
http://en.wikipedia.org/wiki/Yerba_mate
http://en.wikipedia.org/wiki/History_of_yerba_mate
http://www.yerba-mate.com/yerba_mate_history.htm
http://www.rain-tree.com/yerbamate.htm
Yerba Mate is made from Ilex paraguariensis (St. Hil) and is probably the most similar tea to Yaupon black drink.
Yerba Mate infusions are yellow and have a distinct 'tobacco' aroma which are absent in Yaupon decoctions.
Yerba Mate Tea (Ilex paraguariensis): A Comprehensive Review on Chemistry, Health
Implications, and Technological Considerations C.I. HECK AND E.G. DEMEJIA
Journal of Food Science, Vol. 72, Nr. 9, 2007
Dept. of Food Science and Human Nutrition, Univ. of Illinois, Urbana, Champaign, IL 61801
http://www.ncbi.nlm.nih.gov/pubmed/18034743 Heck CI, de Mejia EG. (full text available)
http://amambay.de/wp-content/uploads/2011/11/Heck-Mejia-Yerba-Mate-Tea.pdf (easier site)
Preparation methods of yerba mate, black and green teas are discussed.
Tables of polyphenols and volatile compounds in yerba mate, black and green teas.
Table of saponins found in Ilex species of S.America (adulterants to mate).
Discussion of properties, and potential health effects, and flavors of individual compounds.
Mate is usually prepared by methods that inactivate Polyphenol Oxidase (PPO).
--------------------------
Quantification of saponins in extractive solution of mate leaves (Ilex paraguariensis A. St. Hil.).
http://www.ncbi.nlm.nih.gov/pubmed/20170360 (abstract only)
Assessment of oxidation of leaves of Ilex paraguariensis (St. Hil)
Rochele Fernanda Molin, Alice Teresa Valduga*; Marco Di Luccio; Nessana Dartora; Alexandre José Cichoski; Mônica Pistore; Elisandra Rigo
Universidade Regional Integrada do Alto Uruguai e das Missões, Brasil
Braz. arch. biol. technol. vol.54 no.2 Curitiba Mar./Apr. 2011
http://dx.doi.org/10.1590/S1516-89132011000200016
This work aimed to study the oxidation of leaves of Ilex paraguariensis St. Hil, in a process similar to the oxidation of Camellia sinensis, with the purpose of developing new products based on yerba maté. So far, no previous systematic study about the oxidation of yerba maté has been found elsewhere. A Plackett-Burman experimental design was used for the screening of the significant parameters that affected the oxidation. The oxidation was indirectly quantified by following the changes in the product color, water activity, and pH with the time of processing. The factors that most influenced the process were the age of the leaves and the relative humidity of the oxidation chamber. The differences between the treatments were more evident after 3, 6 12 and 24 h of oxidation. The results could contribute to the developing of new products based on I. paraguariensis St. Hil, increasing the profitability of cultivation of this native species.
http://www.scielo.br/scielo.php?pid=S1516-89132011000200016&script=sci_arttext (full text)
Leaves were dried at 30C before testing.
http://en.wikipedia.org/wiki/Water_activity
http://en.wikipedia.org/wiki/Plackett-Burman_design
-----------------------------------------------------------------------------------------------------------------------------
Flavonol-rich fractions of yaupon holly leaves (Ilex vomitoria, Aquifoliaceae) induce microRNA-146a and have anti-inflammatory and chemopreventive effects in intestinal myofribroblast CCD-18Co cells.
Fitoterapia. 2001 Jun;82(4):557-69
Noratto GD, Kim Y, Talcott ST, Mertens-Talcott SU.
Source Department of Nutrition and Food Science,
Texas A&M University, College Station, TX 77843
This full-length article is available here:
http://www.sensusflavors.com/t-r-pdf/SEN-PR-0012.pdf
and this article discusses biosynthesis of the polyphenols.
http://www.sensusflavors.com/t-r-polyphenolics.html
Quercetin and kaempferol 3-rutinosides were identified in this study
Also mono and di-caffeoylquinic acids were present (same as chlorogenic acid and its isomers).
http://en.wikipedia.org/wiki/Quercetin
http://en.wikipedia.org/wiki/Kaempferol
http://en.wikipedia.org/wiki/Rutinoside
http://en.wikipedia.org/wiki/Chlorogenic_acid
They report these compounds and concentrations for one Yaupon cultivar.
Their extract was 2 g powered leaf infused into 240 mL water at 90C for 30 minutes.
so these are not equivalent to Dr. Duke's Data.
3-caffeoylquinic acid 42.4 mg/L
4-caffeoylquinic acid 28.5 mg/L
5-caffeoylquinic acid 13.1 mg/L
3,4-dicaffeoylquinic acid 3.6 mg/L
3,5-dicaffeoylquinic acid 1.6 mg/L
4,5-didaffeoylquinic acid 15.9 mg/L
Caffeine 14.5 mg/L
Quercetin 3-rutinosides 40.1 mg/L
Kaempferol 3-rutinoside 5.5mg/L
----------------------------------------------------------------------------------------------------------------------------------------
Biosci Biotechnol Biochem. 1998 Jan;62(1):22-7.
Iron chelation by chlorogenic acid as a natural antioxidant.
Kono Y, Kashine S, Yoneyama T, Sakamoto Y, Matsui Y, Shibata H
Department of Life Science and Biotechnology,
Faculty of Life and Environmental Science,
Shimane University, Japan.
Abstract: Chlorogenic acid, a dietary antioxidant, effectively inhibited the iron-induced lipid peroxidation of bovine liver microsomes in a concentration-dependent manner. In the Fenton-type reaction, chlorogenic acid inhibited the production of the hydroxyl radical by iron-EDTA or iron-ADP, while iron plus chlorogenic acid did not generate the hydroxyl radical. The formation of an iron complex with chlorogenic acid was demonstrated by UV/vis absorbance spectroscopic, ESR and 1H-NMR studies. The ferric complex with chlorogenic acid was in the ferric high-spin state near rhombicity, and had no radical scavenging activity. The results indicate that chlorogenic acid prevented the formation of the hydroxyl radical by forming a chelate with iron whose complex cannot catalyze the Fenton-type reaction.
http://www.ncbi.nlm.nih.gov/pubmed/9501514
http://www.jstage.jst.go.jp/article/bbb/62/1/22/_pdf - full text
-------------------------------------------------------------
http://en.wikipedia.org/wiki/Polyphenols_in_tea
http://en.wikipedia.org/wiki/Tannin
http://www.econbot.org/_about_/06_awards/awards_morton/pdfs/a_edwards.pdf
Poster by Adam Edwards (2006?)
Department of Biological Sciences,
Florida International University, Miami, FL
Edwards used HPLC and LC-MS to identify and quantify Caffeine, Theobromine, and Theophylline.
Fresh Yaupon was tinctured in a water-methanol solvent, and chloroform extractions were made from that solution to analyze.
http://en.wikipedia.org/wiki/Caffeine
http://en.wikipedia.org/wiki/Theobromine
http://en.wikipedia.org/wiki/Theophylline
These are the methylated Xanthines: Caffeine, Theobromine, and Theophylline
http://en.wikipedia.org/wiki/Xanthine
------------------------------------------------------
Diversity of Methylxanthine Content in Ilex cassine L. and Ilex vomitoria Ait.:
Assessing Sources of the North American Stimulant Cassina
Adam L. Edwards and Bradley C. Bennett
Center for Ethnobiology and Natural Products,
Department of Biological Sciences, Florida International University, Miami
Economic Botany 59(3):275-285. 2005
doi: 10.1663/0013-0001(2005)059[0275:DOMCII]2.0.CO;2
http://www.bioone.org/doi/abs/10.1663/0013-0001(2005)059%5B0275:DOMCII%5D2.0.CO%3B2
abstract, references, figures, and tables - not full text
includes a table of historical european names for Yaupon and Dahoon
Dahoon (Ilex cassine L.) has more theobromine and less caffeine than Yaupon.
-----------------------------------------------------------------------------------------------------------------------------
Dr. Putz reports in the Gainesville Sun that Yaupon is rich in antioxidants.
http://www.gainesville.com/article/20100408/NEWS/100409426
"UF researchers found that yaupon leaves have the anti-oxidation potential of blueberries. The leaves are chock full of various isomers of chlorogenic acid, coumaric acid, and a cocktail of flavonoids. Concentrations of these compounds, as well as the psychoactives caffeine and theobromine, are especially high in leaves from nitrogen-fertilized females. "
http://en.wikipedia.org/wiki/Flavonoid
http://en.wikipedia.org/wiki/Chlorogenic_acid
---------------------------------------------------------------------------------------------------
Oecologia. 2007 Feb;151(1):1-9. Epub 2006 Oct 18.
Nitrogen fertilizer and gender effects on the secondary metabolism of yaupon, a caffeine-containing North American holly.
Palumbo MJ, Putz FE, Talcott ST.
Department of Botany, University of Florida, Gainesville, FL
http://www.springerlink.com/content/kn682u522p5nj26g/
identifies cinnamic acid derivatives...
http://en.wikipedia.org/wiki/Cinnamic_acid
http://en.wikipedia.org/wiki/Coumaric_acid
Briefly, Palumbo shows that Yaupon plants that receive extra nitrogen exhibit increases in foliar concentrations of caffeine, but not phenolic and other compounds. Further they show that female Yaupon plants have larger increases of caffeine concentrations than male plants in response to fertilization. Also examines antioxidant potentials of Yaupon plants.
--------------------------------------------------------------------------------------------------------------------------------
YERBA MATE, Ilex paraguariensis
http://en.wikipedia.org/wiki/Yerba_mate
http://en.wikipedia.org/wiki/History_of_yerba_mate
http://www.yerba-mate.com/yerba_mate_history.htm
http://www.rain-tree.com/yerbamate.htm
Yerba Mate is made from Ilex paraguariensis (St. Hil) and is probably the most similar tea to Yaupon black drink.
Yerba Mate infusions are yellow and have a distinct 'tobacco' aroma which are absent in Yaupon decoctions.
Yerba Mate Tea (Ilex paraguariensis): A Comprehensive Review on Chemistry, Health
Implications, and Technological Considerations C.I. HECK AND E.G. DEMEJIA
Journal of Food Science, Vol. 72, Nr. 9, 2007
Dept. of Food Science and Human Nutrition, Univ. of Illinois, Urbana, Champaign, IL 61801
http://www.ncbi.nlm.nih.gov/pubmed/18034743 Heck CI, de Mejia EG. (full text available)
http://amambay.de/wp-content/uploads/2011/11/Heck-Mejia-Yerba-Mate-Tea.pdf (easier site)
Preparation methods of yerba mate, black and green teas are discussed.
Tables of polyphenols and volatile compounds in yerba mate, black and green teas.
Table of saponins found in Ilex species of S.America (adulterants to mate).
Discussion of properties, and potential health effects, and flavors of individual compounds.
Mate is usually prepared by methods that inactivate Polyphenol Oxidase (PPO).
--------------------------
Quantification of saponins in extractive solution of mate leaves (Ilex paraguariensis A. St. Hil.).
http://www.ncbi.nlm.nih.gov/pubmed/20170360 (abstract only)
Assessment of oxidation of leaves of Ilex paraguariensis (St. Hil)
Rochele Fernanda Molin, Alice Teresa Valduga*; Marco Di Luccio; Nessana Dartora; Alexandre José Cichoski; Mônica Pistore; Elisandra Rigo
Universidade Regional Integrada do Alto Uruguai e das Missões, Brasil
Braz. arch. biol. technol. vol.54 no.2 Curitiba Mar./Apr. 2011
http://dx.doi.org/10.1590/S1516-89132011000200016
This work aimed to study the oxidation of leaves of Ilex paraguariensis St. Hil, in a process similar to the oxidation of Camellia sinensis, with the purpose of developing new products based on yerba maté. So far, no previous systematic study about the oxidation of yerba maté has been found elsewhere. A Plackett-Burman experimental design was used for the screening of the significant parameters that affected the oxidation. The oxidation was indirectly quantified by following the changes in the product color, water activity, and pH with the time of processing. The factors that most influenced the process were the age of the leaves and the relative humidity of the oxidation chamber. The differences between the treatments were more evident after 3, 6 12 and 24 h of oxidation. The results could contribute to the developing of new products based on I. paraguariensis St. Hil, increasing the profitability of cultivation of this native species.
http://www.scielo.br/scielo.php?pid=S1516-89132011000200016&script=sci_arttext (full text)
Leaves were dried at 30C before testing.
http://en.wikipedia.org/wiki/Water_activity
http://en.wikipedia.org/wiki/Plackett-Burman_design
-----------------------------------------------------------------------------------------------------------------------------
Flavonol-rich fractions of yaupon holly leaves (Ilex vomitoria, Aquifoliaceae) induce microRNA-146a and have anti-inflammatory and chemopreventive effects in intestinal myofribroblast CCD-18Co cells.
Fitoterapia. 2001 Jun;82(4):557-69
Noratto GD, Kim Y, Talcott ST, Mertens-Talcott SU.
Source Department of Nutrition and Food Science,
Texas A&M University, College Station, TX 77843
This full-length article is available here:
http://www.sensusflavors.com/t-r-pdf/SEN-PR-0012.pdf
and this article discusses biosynthesis of the polyphenols.
http://www.sensusflavors.com/t-r-polyphenolics.html
Quercetin and kaempferol 3-rutinosides were identified in this study
Also mono and di-caffeoylquinic acids were present (same as chlorogenic acid and its isomers).
http://en.wikipedia.org/wiki/Quercetin
http://en.wikipedia.org/wiki/Kaempferol
http://en.wikipedia.org/wiki/Rutinoside
http://en.wikipedia.org/wiki/Chlorogenic_acid
They report these compounds and concentrations for one Yaupon cultivar.
Their extract was 2 g powered leaf infused into 240 mL water at 90C for 30 minutes.
so these are not equivalent to Dr. Duke's Data.
3-caffeoylquinic acid 42.4 mg/L
4-caffeoylquinic acid 28.5 mg/L
5-caffeoylquinic acid 13.1 mg/L
3,4-dicaffeoylquinic acid 3.6 mg/L
3,5-dicaffeoylquinic acid 1.6 mg/L
4,5-didaffeoylquinic acid 15.9 mg/L
Caffeine 14.5 mg/L
Quercetin 3-rutinosides 40.1 mg/L
Kaempferol 3-rutinoside 5.5mg/L
----------------------------------------------------------------------------------------------------------------------------------------
Biosci Biotechnol Biochem. 1998 Jan;62(1):22-7.
Iron chelation by chlorogenic acid as a natural antioxidant.
Kono Y, Kashine S, Yoneyama T, Sakamoto Y, Matsui Y, Shibata H
Department of Life Science and Biotechnology,
Faculty of Life and Environmental Science,
Shimane University, Japan.
Abstract: Chlorogenic acid, a dietary antioxidant, effectively inhibited the iron-induced lipid peroxidation of bovine liver microsomes in a concentration-dependent manner. In the Fenton-type reaction, chlorogenic acid inhibited the production of the hydroxyl radical by iron-EDTA or iron-ADP, while iron plus chlorogenic acid did not generate the hydroxyl radical. The formation of an iron complex with chlorogenic acid was demonstrated by UV/vis absorbance spectroscopic, ESR and 1H-NMR studies. The ferric complex with chlorogenic acid was in the ferric high-spin state near rhombicity, and had no radical scavenging activity. The results indicate that chlorogenic acid prevented the formation of the hydroxyl radical by forming a chelate with iron whose complex cannot catalyze the Fenton-type reaction.
http://www.ncbi.nlm.nih.gov/pubmed/9501514
http://www.jstage.jst.go.jp/article/bbb/62/1/22/_pdf - full text
-------------------------------------------------------------
http://en.wikipedia.org/wiki/Polyphenols_in_tea
http://en.wikipedia.org/wiki/Tannin
Chlorogenic Acid and Caffeoylquinic (CQA) Compounds
Confirmation that the Maillard reaction is the principle contributor to the antioxidant capacity of coffee brews
Yazheng Liu, David D. Kitts
Food, Nutrition and Health Department, Faculty of Land and Food Systems,
University of British Columbia, 2205 East Mail, Vancouver, BC, Canada V6T 1Z4
http://dx.doi.org/10/1016/j.foodres.2010.12.037
Abstract only:
Chemical characteristics related to the antioxidant activity of roasted coffee
(RC) were evaluated, using non-roasted coffee beans (NRC) and model Maillard
reaction products (MRPs) as controls. The formation of MRPs and the degradation
of phenolics in RC were characterized by employing a battery of fluorescence,
UV–vis spectra and tri-stimulus color parameters measured on NRC, RC and the
model MRPs. Total chlorogenic acid (CGA) and caffeine contents
in NRC and RC extracts were also quantified using HPLC. Both RC and controls
showed high antioxidant activity in three chemical based assays irrespective of
caffeine content. Data from this study suggested that natural phenolics present
in NRC had higher antioxidant activity compared to MRPs derived from coffee and
model MR systems. However, MRPs were the prevailing antioxidants in RC as free
CGA was lost (> 90%). The mechanisms of the antioxidant action associated
with coffee MRPs involved hydrogen atom transfer and single electron transfer
mechanisms.
http://www.sciencedirect.com/science/article/pii/S0963996911000093
Coffee's Bitter Mysteryhttp://news.sciencemag.org/sciencenow/2007/08/21-01.html
Roasting coffee causes Chlorogenic Acid (CGA) to form Chlorogenic Acid Lactones (CGL), and further breakdown products called phenylindanes - CGL is bitter, phenylindanes are very bitter.
Effect of Roasting on the Formation of Chlorogenic Acid Lactones in Coffee
Journal of Agricultural and Food Chemistry 2005, 53, 1505−1513,
ADRIANA FARAH, TOMAS DE PAULIS, LUIZ C. TRUGO, AND PETER R. MARTIN
http://vanderbilt.edu/ics/Files/Effect%20of%20Roasting%20on%20lactones.pdf
The enzymic oxidation of chlorogenic acid and some reactions of the quinone produced.
Biochem J. 1966 Feb;98(2):567-80. Pierpoint WS
http://www.ncbi.nlm.nih.gov/pubmed/5941350
o-Quinones formed in plant extracts. Their reactions with amino acids and peptides.
Biochem J. 1969 May; 112(5): 609–616. W. S. Pierpoint
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC1187763/
Chlorogenic Acid Compounds from Coffee Are Differentially Absorbed and Metabolized in Humans
Mariana Monteiro, Adriana Farah, Daniel Perrone, Luiz C. Trugo, Carmen Donangelo
Journal of Nutrition. J. Nutr. October 2007 vol. 137 no. 10 2196-2201
http://jn.nutrition.org/content/137/10/2196.full
Uses HPLC to measures 3-CQA, 4-CQA, 5-CQA, 3,4-diCQA, 3,5-diCQA, 4,5-diCQA and related compounds in plasma from six individuals after drinking coffee. Several different metabolic profiles observed - study needs a larger population. Most CQA metabolites were not eliminated with urine.
[Advances in caffeoylquinic acid research]. [Article in Chinese]
Zhongguo Zhong Yao Za Zhi. 2006 Jun;31(11):869-74.
Zhao Y [[email protected]], Zhao J, Li XP, Zhou CX, Sun HD, Hao XJ, Xiao PG.
College of Pharmaceutical Science, Zhejiang University, Hangzhou 310031, China.
Abstract This paper reviewed updated research progresses of caffeoylquinic acids both in phytochemical and pharmacological aspects. The resources, distribution as well as the chemical structures of monocaffeoylquinic acids, dicaffeoylquinic acids, tricaffeoylquinic acids and multicaffeoylquinic acids are conclusively analyzed. The reviewed pharmacological investigations indicated that the caffeoylquinic acids exhibited significant activities such as anti-oxidation, anti-inflammation, enzyme inhibition, hypatoprotective and anti-PAF effects. The broad distribution and the remarkably pharmacological activities of these natural phenolic acids indicated their potential in the discovery and development of new natural drugs.
Antibacterial activity and mechanism of action of chlorogenic acid.
J Food Sci. 2011 Aug;76(6):M398-403. doi: 10.1111/j.1750-3841.2011.02213.x. Epub 2011 Jun 2.
Lou Z, Wang H, Zhu S, Ma C, Wang Z.
State Key Laboratory of Food Science and Technology, School of Food Science and Technology, Jiangnan Univ., Wuxi 214122, PR China. [email protected]
Abstract In this study, the antibacterial activity and mechanism of action of chlorogenic acid against bacteria were assessed. The data from minimum inhibitory concentration (MIC) values showed that chlorogenic acid effectively inhibited the growth of all tested bacterial pathogens, and the MIC values were ranging from 20 to 80 μg/mL. An investigation into action mode of chlorogenic acid against the pathogen indicated that chlorogenic acid significantly increased the outer and plasma membrane permeability, resulting in the loss of the barrier function, even inducing slight leakage of nucleotide. The leakage of cytoplasmic contents was also observed by electron micrographs. These results supported our hypothesis that chlorogenic acid bound to the outer membrane, disrupted the membrane, exhausted the intracellular potential, and released cytoplasm macromolecules, which led to cell death.
Antihypertensive effects and mechanisms of chlorogenic acids.
Hypertens Res. 2012 Apr;35(4):370-4. doi: 10.1038/hr.2011.195. Epub 2011 Nov 10.
Zhao Y, Wang J, Ballevre O, Luo H, Zhang W.
Nestle Research Center Beijing, No. 5 DiJin Road, Beijing, China.
Abstract Chlorogenic acids (CGAs) are potent antioxidants found in certain foods and drinks, most notably in coffee. In recent years, basic and clinical investigations have implied that the consumption of chlorogenic acid can have an anti-hypertension effect. Mechanistically, the metabolites of CGAs attenuate oxidative stress (reactive oxygen species), which leads to the benefit of blood-pressure reduction through improved endothelial function and nitric oxide bioavailability in the arterial vasculature. This review article highlights the physiological and biochemical findings on this subject and highlights some remaining issues that merit further scientific and clinical exploration. In the framework of lifestyle modification for the management of cardiovascular risk factors, the dietary consumption of CGAs may hold promise for providing a non-pharmacological approach for the prevention and treatment of high blood pressure.
Chlorogenic acid ameliorates brain damage and edema by inhibiting matrix metalloproteinase-2 and 9 in a rat model of focal cerebral ischemia.
Eur J Pharmacol. 2012 Aug 15;689(1-3):89-95. Epub 2012 May 31.
Lee K, Lee JS, Jang HJ, Kim SM, Chang MS, Park SH, Kim KS, Bae J, Park JW, Lee B, Choi HY, Jeong CH, Bu Y.
College of Oriental Medicine, Kyung Hee University, Seoul 130 701, Republic of Korea.
Abstract Chlorogenic acid (CGA) has been reported to have various beneficial effects on the cardiovascular and central nervous systems. The purpose of the current study was to investigate whether CGA has protective effects against cerebral ischemia and whether these effects are due to modification of brain edema-related vascular factors. In a rat model of transient middle cerebral artery occlusion (MCAo, 2h of occlusion followed by 22h of reperfusion), we measured infarct volume and performed behavioral test to evaluate the effects of CGA on brain damage and sensory-motor functional deficits. Brain water content and Evans blue extravasation were measured to evaluate brain edema and blood brain barrier (BBB) damage. Lipid peroxidation (LPO) and the expressions and activities of matrix metalloproteinase (MMP)-2 and MMP-9 were measured to investigate the mechanisms of action. Intraperitoneal injection of CGA (3, 10, and 30mg/kg) at 0h and 2h after MCAo dose-dependently reduced infarct volume and sensory-motor functional deficits. It also reduced brain water content and Evans blue extravasation. Mechanistically, CGA reduced LPO and MMPs expressions and activities. These results suggest that CGA reduces brain damage, BBB damage and brain edema by radical scavenging activity and the inhibitory effects on MMP-2 and MMP-9.
Chlorogenic Acid Exhibits Cholesterol Lowering and Fatty Liver Attenuating Properties by Up-regulating the Gene Expression of PPAR-α in Hypercholesterolemic Rats Induced with a High-Cholesterol Diet.
Phytother Res. 2012 Jun 6. doi: 10.1002/ptr.4751. [Epub ahead of print]
Wan CW, Wong CN, Pin WK, Wong MH, Kwok CY, Chan RY, Yu PH, Chan SW.
Food Safety and Technology Research Centre, Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hong Kong, SAR, China.
Abstract Hypercholesterolemia is a major risk factor for the development of cardiovascular disease and nonalcoholic fatty liver disease. Natural compounds have been proved to be useful in lowering serum cholesterol to slow down the progression of cardiovascular disease and nonalcoholic fatty liver disease. In the present study, the hypocholesterolemic and hepatoprotective effects of the dietary consumption of chlorogenic acid were investigated by monitoring plasma lipid profile (total cholesterol, triglycerides, high-density lipoprotein and low-density lipoprotein) in Sprague-Dawley rats fed with a normal diet, a high-cholesterol diet or a high-cholesterol diet supplemented with chlorogenic acid (1 or 10 mg/kg/day p.o.) for 28 days. Chlorogenic acid markedly altered the increased plasma total cholesterol and low-density lipoprotein but decreased high-density lipoprotein induced by a hypercholesterolemic diet with a dose-dependent improvement on both atherogenic index and cardiac risk factor. Lipid depositions in liver were attenuated significantly in hypercholesterolemic animals supplemented with chlorogenic acid. It is postulated that hypocholesterolemic effect is the primary beneficial effect given by chlorogenic acid, which leads to other secondary beneficial effects such as atheroscleroprotective, cardioprotective and hepatoprotective functions. The hypocholesterolemic functions of chlorogenic acid are probably due to the increase in fatty acids unitization in liver via the up-regulation of peroxisome proliferation-activated receptor α mRNA.
Chlorogenic acid inhibits LPS-induced microglial activation and improves survival of dopaminergic neurons.
Brain Res Bull. 2012 Aug 1;88(5):487-94. Epub 2012 May 2.
Shen W, Qi R, Zhang J, Wang Z, Wang H, Hu C, Zhao Y, Bie M, Wang Y, Fu Y, Chen M, Lu D.
Department of Pathophysiology, School of Medicine, Jinan University, Guangzhou, Guangdong 510632, China.
Abstract Pro-inflammatory factors released by activated microglia may contribute to the progression of neurodegenerative diseases. As a natural phenolic acid, chlorogenic acid (CGA) has been shown to have anti-inflammatory properties. However, it is unclear whether CGA has the ability to mediate microglial activation. The present study investigated the role of CGA in lipopolysaccharide (LPS)-stimulated microglia. Our data demonstrated that CGA significantly suppressed NO production and TNF-α release in LPS-stimulated primary microglia. In addition, CGA decreased LPS-stimulated phosphorylation and degradation of inhibitory kappa B-alpha (IκBα), and prevented translocation of nuclear factor-kappaB (NF-κB). Furthermore, CGA prevented neurotoxicity caused by microglial activation and ultimately improved survival of dopaminergic (DA) neuron. Finally, in vivo data showed that CGA pretreatment attenuated LPS-induced IL-1β and TNF-α release in substantia nigra (SN). Our results suggested that the pretreatment of CGA significantly inhibits the microglial activation, and CGA may be neuroprotective for pro-inflammatory factor-mediated neurodegenerative disorders.
Chlorogenic acid stimulates glucose transport in skeletal muscle via AMPK activation: a contributor to the beneficial effects of coffee on diabetes.
PLoS One. 2012;7(3):e32718. Epub 2012 Mar 7. Ong KW, Hsu A, Tan BK.
Department of Pharmacology, Yong Loo Lin School of Medicine, National University of Singapore, Singapore, Singapore.
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC3296733/ - full text online
Espresso coffees, caffeine and chlorogenic acid intake: potential health implications.
Food Funct. 2012 Jan;3(1):30-3. Epub 2011 Nov 30. Crozier TW, Stalmach A, Lean ME, Crozier A.
School of Medicine, College of Medical, Veterinary and Life Sciences, Joseph Black Building, University of Glasgow, Glasgow, G12 8QQ, UK.
Abstract HPLC analysis of 20 commercial espresso coffees revealed 6-fold differences in caffeine levels, a 17-fold range of caffeoylquinic acid contents, and 4-fold differences in the caffeoylquinic acid : caffeine ratio. These variations reflect differences in batch-to-batch bean composition, possible blending of arabica with robusta beans, as well as roasting and grinding procedures, but the predominant factor is likely to be the amount of beans used in the coffee-making/barista processes. The most caffeine in a single espresso was 322 mg and a further three contained >200 mg, exceeding the 200 mg day(-1) upper limit recommended during pregnancy by the UK Food Standards Agency. This snap-shot of high-street expresso coffees suggests the published assumption that a cup of strong coffee contains 50 mg caffeine may be misleading. Consumers at risk of toxicity, including pregnant women, children and those with liver disease, may unknowingly ingest excessive caffeine from a single cup of espresso coffee. As many coffee houses prepare larger volume coffees, such as Latte and Cappuccino, by dilution of a single or double shot of expresso, further study on these products is warranted. New data are needed to provide informative labelling, with attention to bean variety, preparation, and barista methods.
Inhibition of platelet aggregation by chlorogenic acid via cAMP and cGMP-dependent manner.
Blood Coagul Fibrinolysis. 2012 Aug 8. [Epub ahead of print] Cho HJ, Kang HJ, Kim YJ, Lee DH, Kwon HW, Kim YY, Park HJ. Source aDepartment of Biomedical Laboratory Science, College of Medical Science, Konyang University, Gasuwon-dong, Seo-gu, Daejeon bDepartment of Biomedical Laboratory Science, College of Biomedical Science and Engineering and Regional Research Center, Inje University, Obang-dong, Gimhae, Gyungnam, Republic of Korea *Hyun-Jeong Cho and Hee-Jin Kang contributed equally to this work.
Abstract In this study, we investigated the effect of chlorogenic acid, a phenolic acid, on collagen (10 μg/ml)-stimulated platelet aggregation. Chlorogenic acid dose-dependently inhibited collagen-induced platelet aggregation, and suppressed the production of thromboxane A2 (TXA2), an intracellular Ca-agonist as an aggregation-inducing autacoidal molecule, which was associated with the strong inhibition of cyclooxygenase (COX)-1 in platelet microsomes having cytochrome c reductase activity. In addition, chlorogenic acid increased significantly the formation of cyclic adenosine monophosphate (cAMP) and cyclic guanosine monophosphate (cGMP), intracellular Ca-antagonists as aggregation-inhibiting molecules. These results suggest that chlorogenic acid has antiplatelet activity through the reduction of TXA2 and the increase of cAMP and cGMP levels. Therefore, our data demonstrate that chlorogenic acid is a potent inhibitor of collagen-stimulated platelet aggregation, and may be a crucial tool for a negative regulator during platelet activation in thrombotic diseases.
Protective effects of chlorogenic acid against ischemia/reperfusion injury in rat liver: molecular evidence of its antioxidant and anti-inflammatory properties.
J Nutr Biochem. 2011 Dec 29. [Epub ahead of print] Yun N, Kang JW, Lee SM.
Abstract Hepatic ischemia and reperfusion injury (I/R) is accompanied by excessive reactive oxygen species and resultant sterile inflammation. Chlorogenic acid (CGA), one of the most abundant polyphenols in the human diet, has been shown to exert potent anti-inflammatory, antibacterial and antioxidant activities. Thus, the purpose of the present study was to investigate protective effects of CGA and its molecular mechanisms against hepatic I/R injury. Rats were subjected to 60 min of partial hepatic ischemia followed by 5 h of reperfusion. CGA (2.5, 5 and 10 mg/kg, ip) was administered twice: 10 min prior to ischemia and 10 min before reperfusion. CGA treatment resulted in marked improvement of hepatic function and histology, and suppressed oxidative stress, as indicated by hepatic lipid peroxidation and glutathione level. Levels of serum tumor necrosis factor-α, inducible nitric oxide synthase and cyclooxygenase-2 protein and mRNA expressions were up-regulated after I/R; these effects were attenuated by CGA. Immunoblot results showed that CGA reduced I/R-induced toll-like receptor 4 overexpression, nuclear translocation of nuclear factor kappa B and interferon regulatory factor-1, high-mobility group box-1 release into extracellular milieu, and enhanced heme oxygenase-1 expression and nuclear translocation of nuclear factor erythroid 2-related factor 2. Our results suggest that CGA alleviates I/R-induced liver injury and that this protection is likely due to inhibition of inflammatory response and enhancement of antioxidant defense systems. Therefore, CGA might have potential as an agent for use in clinical treatment of hepatic I/R injury.
The Coffee Constituent Chlorogenic Acid Induces Cellular DNA Damage and Formation of Topoisomerase I- and II-DNA Complexes in Cells.
J Agric Food Chem. 2012 Jul 24. [Epub ahead of print] Burgos-Morón E, Calderón-Montaño JM, Orta ML, Pastor N, Pérez-Guerrero C, Austin C, Mateos S, López-Lázaro M.
Department of Pharmacology, Faculty of Pharmacy, University of Seville , Seville, Spain.
Abstract Chlorogenic acid (CGA) is a plant polyphenol with known antioxidant properties. Although some studies suggest that CGA has anticancer properties, others indicate that this dietary constituent may cause DNA damage and induce carcinogenic effects. Because CGA is widely consumed in the form of coffee, it is important to further evaluate the putative DNA-damaging activity of CGA. Here we have employed two standard techniques commonly used for DNA damage detection (the comet assay and the γ- H2AX focus assay) and observed that CGA (0.5-5 mM) induces DNA damage in normal and cancer cells. We report for the first time that CGA induces high levels of topoisomerase I- and topoisomerase II-DNA complexes in cells (TARDIS assay). Catalase pretreatment abolished the formation of these topoisomerase-DNA complexes and reduced the cytotoxic activity of CGA, therefore indicating that hydrogen peroxide plays an important role in these activities. Lung cancer cells (A549) were more sensitive than normal lung fibroblasts (MRC5) to the cytotoxic activity of CGA, supporting previous findings that CGA may induce selective killing of cancer cells. Taking into consideration our results and the pharmacokinetic profile of CGA, the possible cancer preventive, carcinogenic and therapeutic potential of this dietary agent are discussed.
Energy dissipation and radical scavenging by the plant phenylpropanoid pathway.
Stephen C. Grace and Barry A. Logan
Biodynamics Institute, 711 Choppin Hall, Louisiana
State University, Baton Rouge, LA 70803-18 00, USA
Department of Biology, Bowdoin College, Brunswick, MA 04011, USA
Phil. Trans. R. Soc. Lond. B 2000 355, 1499-1510
doi: 10.1098/rstb.2000.0710
http://rstb.royalsocietypublishing.org/content/355/1402/1499.full.pdf
Has interesting data on CGA redox reactions including spectra & esr, and has diagrams of plant metabolic pathways, explains how plants use CGA to deal with oxidative stresses.