Human uses of phytochemicals Secondary plant chemistry and natural products Definition of plant secondary metabolites Basic kinds of plant 2º metabolites characteristics and examples of each Ethnomedicine / ethnopharmocognacy

What are plant secondary metabolites? Contrast with primary metabolites 1º metabolites are in all cells of all kinds of plants required for basic functioning of cells carbohydrates, proteins, lipids, nucleic acids Secondary metabolites 2º metabolites are in some but not all plant groups a left-over term from an old-fashioned concept previously thought to be waste products but have various functions in the plant: respond to environment plant defense against herbivores pathogens competitors protection from damaging radiation from sunlight

Secondary metabolites glycosides (some compounds of the classes below may also be glycosides) phenolics terpenoids nitrogen-containing compounds sulfur-containing compounds Note that these basic kinds can overlap; they are not exclusive categories.

glycosides composed of glycone + aglycone sugar part + active portion active once hydrolysed (broken down) some require specialized bacteria in large intestine to hydrolyse them and release the active portion some kinds are toxic: Cyanogenic glycosides (releases cyanide) Cardiac glycosides (affect rhythm and strength of heartbeats)

Digitalis Cardiac glycoside English folk healers used to treat “dropsy” (edema, fluid accumulation due to inadequate pumping of heart) mentioned in Gerard’s herbal 1596 William Withering 1775 learned from “an old woman in Shropshire” dosage problems! source of cardiac glycosides digitoxin and digoxin, used to treat heart failure and heart arrhythmia Francis Gwyn Jones www.forestryimages.org Barbara Tokarska-Guzik, University of Silesia, www.forestryimages.org

Phenolics Aromatic ring with at least one hydroxyl group (aromatic alcohols) Simple phenols are antibacterial, antiseptic, anthelmintic Salicylic acid and salicylates: salicin, methyl salicylate are found in what plants? Acetylsalicylic acid (synthetic derivative) = ? Warfarin (UW-Madison connection) Flavors, essential oils (e.g., thymol) phenol http://www.arthurleej.com/images/gaultheria.jpg

Polyphenols: Antioxidants in red wine and green tea proanthocyanidins or resveratrol? http://prospect.rsc.org/blogs/cw/2008/08/

Polyphenols: Tannins High molecular weight Astringent May bind with proteins (enzymes) Some kinds reduce inflammation and bleeding http://newparadigmdigest.com/2099/acorn/

Polyphenols: Flavonoids Sometimes called “bioflavonoids” May be free or glycosides Plant pigments Anthocyanins (red and blue pigments) UV protection for plant Antioxidant, scavenging of free radicals Protect collagen from inflammation Plant response to injury (phytoalexins) http://i.telegraph.co.uk/telegraph/multimedia/archive/01068/gardening-graphics_1068112a.jpg http://www.enflower.org/entry/blueberries-for-beauty-and-taste/

Terpenoids Based on isoprene subunits aromatics – volatile molecules http://www.benbest.com/nutrceut/phytochemicals.html Terpenoids Based on isoprene subunits aromatics – volatile molecules some plant hormones gibberellin, abscisic acid carotenoids: carotenes & xanthophylls tetraterpenoids (8 isoprene units) -carotene, lycopene, lutein  zeaxanthin images from Wikipedia

Terpenoids rubber (poly-isoprene) steroids saponins natural detergents http://www.benbest.com/nutrceut/phytochemicals.html Terpenoids rubber (poly-isoprene) steroids saponins natural detergents names: soapwort, soaproot, etc. some toxins, some health claims Why is Saponaria officinalis called “Bouncing Bet”? http://www.heritagevillagecincinnati.org/ http://www.ct-botanical-society.org/galleries/saponariaoffi.html

Sulphur-containing compounds glucosinolates (mustard oil glycosides) Brassicaceae and other related families garden nasturtium Tropaeolum condiments: mustard, horseradish anti-cancer effects of Brassica antibiotic effects but also anti-thyroid effects – livestock poisoning http://serc.carleton.edu/genomics/units/brassica_photos.html http://www.sogoodblog.com/wp-content/uploads/2009/06/mustard.jpg

Sulphur-containing compounds disulphides onions, garlic, & other Allium species includes "lacrimatory factor" antimicrobial effects reduce blood clotting http://www.garlicbreakthrough.com/garlic.jpg http://blogs.sfweekly.com/foodie/green-onion-01.jpg http://www.iscco.org/category/herbal-medicine/onion

Asafoetida Plant of the Day Ferula assa-foetida (Ferula foetida) Plant family? Merde du Diable (Fr), Devil's Dung Used in Indian cuisine, especially by Jains (Why?) Oleo-gum-resin disulfides vs. flu

Nitrogen-containing compounds Cyanogenic glycosides produce hydrocyanic acid when broken down Amygdalin  HCN + benzaldehyde common in Rosaceae cassava processing to detoxify http://en.wikipedia.org/wiki/File:Mandel_Gr_99.jpg http://www.callabletreeservice.com/images/cherry_tree.jpg http://seekingsustenance.files.wordpress.com/2010/04/manioc-whole.jpg

Nitrogen-containing compounds Alkaloids bitter, alkaline may be toxic or psychoactive caffeine, nicotine, solanine and many others

Caffeine-producing plants Alkaloids Caffeine-producing plants coffee chocolate tea cola nut yerba mate guaraná http://www.fundaj.gov.br/docs/iesam/mhn/guarana.jpg http://waynesword.palomar.edu/images/yerbam5.gif http://www.herbsarespecial.com.au/pics/yerba-mate.jpg http://www.plantoftheweek.org/image/camellia.jpg http://www.tea-a.gr.jp/images/ind_img_02.jpg http://www.fieldmuseum.org/chocolate/about.html

Alkaloids Erythroxylum coca

Coca – Erythroxylum coca Alkaloids Coca – Erythroxylum coca source of cocaine traditionally chewed with an alkaline substance in Andes (e.g., ashes) brewed as herb tea legal in Peru and Bolivia

Coca – Erythroxylum coca Alkaloids Coca – Erythroxylum coca source of cocaine Coca cola history coca wine Freud, Sherlock Holmes Coca Cola invented in 1885 What was the purpose? How did it change in 1904?

Coca – Erythroxylum coca Alkaloids Coca – Erythroxylum coca Evo Morales, president of Bolivia appealed to UN to lift international ban promotes coca leaf products as alternative to illegal trade http://www.zentastic.com/blog/2006/09/27/coca-and-the-gym/ http://www.telegraph.co.uk/news/worldnews/southamerica/bolivia/8270448/Spain-backs-Bolivia-in-coca-leaf-campaign.html

Quinine from Cinchona Alkaloids alkaloid quinine isolated from cinchona bark in 1820. synthesized in the laboratory 1944 chloroquine and primaquine but resistant strains Illustration of “Kinquina” from Pierre Pomet, Histoire generale des drogues. Paris: Jean Baptiste Loyson & Augustin Pillon, 1694, p. 132.

Rosy periwinkle Alkaloids Vincristine and vinblastine and many other alkaloids chemotherapy for childhood leukemia, Hodgkin's disease, and other cancers Catharanthus roseus Madagascar native now naturalized around tropics and subtropics and cultivated as an annual ornamental in temperate areas.

Opium poppy - Papaver somniferum Alkaloids Opium poppy - Papaver somniferum morphine, codeine and other alkaloids heroin - a synthetic derivative of morphine http://www.dkimages.com/discover/previews/871/20148577.JPG What were the “Opium Wars” during 1839 to 1842 and 1856 to 1860 fought over? http://flickr.com/photos/superfantastic/

Peyote Alkaloids Lophophora williamsii, L. diffusa mescaline and other psychoactive alkaloids http://www.dkimages.com/

Ethnomedicine / ethnopharmocognacy random screens vs. targeted taxonomic ecological ethnobotanical HIV example from chapter of Walter Lewis: 15/50 (30%) vs. 1,429/16,886 (8.5%)

Taxol from Taxus spp. One success from modified random scan. important for cancer chemotherapy http://www.phcog.org/Taxus/Taxus_Web.html

Synergy Interaction in which combined effect is greater than the sum of the parts. May include interaction of different herbs in formulas or different constituents within the same herb.

plant 2º metabolites phenol subunits isoprene subunits nitrogen sulfur glycone and aglycone

Secondary metabolites phenolics terpenoids nitrogen-containing compounds sulfur-containing compounds glycosides (may overlap with the above)