Secondary Metabolism Primary & Secondary metabolites Primary Metabolites: Secondary Metabolites: Sugar, starch, citric acid, Vitamines Pectins & algins (food additives) Phenolic compounds (coffee, vine, incense, perfumes) protein (seeds of Fabaeceae) Terpenoid compounds plant fatty oils (nuts, corn, (lemon scent, anis taste, bitter sesame, peanuts, sunflower, rape) taste of hops, tonic water, color cellulose (cotton, fiber, wood) Amines (smell of fish, algae, ) Alkaloids (coffeine etc.) Glycosides (Sinigrin from mustard, allicin from garlic, PEA in chocolate) Doctrine of Signatures The doctrine of signatures states that herbs that resemble various parts of the body can be used to treat ailments of that part of the body. Examples include the plants liverwort; snakeroot: an antidote for snake venom; lungwort; bloodroot; toothwort; and wormwood, to expel intestinal parasites. A theological justification was “The Almighty must have set his sign upon the various means of curing disease which he provided”. However some version of the doctrine exists also among Asians & Native Americans.

Medicinal plants based on the "Doctrine of Signatures" in Porta's Phytognomonica.

Plants for scaly diseases include pine cones, thistles, catkins, and lily bulbs. The snake and fish were added to show scaly skin. Doctrine of Signatures The doctrine of signatures was described in the book “Phytognomica” by Philippus, Aureolus Theophrastus Bombastus von Hohenhein called . It provided many of the common names for plants

St Johns Wort Hypericum perfor : holes in the leaf indicate use for cuts (Paracelsus) liverwort; Hepatica heals liver diseases snakeroot Ageratina altissima in the Asters contains toxin tremetol (milk sicknes) helps against snake venom lungwort; Pulmonaria spotted leaves excellent remedy for tuberculosis bloodroot; Sanguinaria canadensis wormwood Artemisia absinthum was used to expel intestinal parasites. Feverfew Chrysanthemum parthenium was used accordingly Eyebright Euphrasia officinalis was excellent remedy for sore eyes Toothwort Lathrea squamaria was used together with pine cones to fight toothaches is a carnivorous chlorophyll-free plant Clelandine Chelidonium major has yellow juice against jaundice No doctrine but signatures Î Plants have glands

Clear giveaways = signatures = anatomical clues that plants have sequestered lots of active compounds Î glandular trichomes, lacticifers, idioblasts, resin canals, floral & extrafloral nectaries Anatomical signatures Î glandular hairs Clear giveaways = signatures = anatomical clues that plants have sequestered lots of active compounds Î (1) glandular trichomes, (2) lacticifers, idioblasts,(3) resin canals, (4) floral & extrafloral nectaries Trichomes or hairs are fine outgrowths or appendages on Examples are hairs, glandular hairs, scales, and papillae.

Drosera leaf Coleus leaf

Cross section through stem of Digitalis Leaf surface trichomes (Salvia divinorum). The upper leaf surface contains numerous or foxglove plant shows glandular hair. multicellular, glandular and non-glandular trichomes (hairs). . Stinging Hairs For a long time we did not know what caused the stinging sensation of Urtica dioica? It was first shown that formic acid was inside the hairs but that alone does not cause such effects! pict Urtica dioica is harmless when compared with tropical nettles like Urtica stimulans (Java) & Urtica crenulata (India) & the worst Urtica urentissima (Timor) which also cause skin irritations but in addition affect the nervous system in the area with paralytic cramps & permanent damage to nerves. Dogs refuse to search for game after experiencing the burning sensation of nettels, geese seem to be insensitive, larvae of some butterfly too There are other plant families with stinging hairs Hydrophyllaeceae Wigandia urens , Euphorbiaceae Jatropha urens have stinging hairs while many members of the Urticaeceae (glass plants, hops) have none. Other plants like Primula obconica cause dermatitis

Mimicry of nettle leaves by dead nettels alias Lamium species Secrets of Secretion of glandular hairs Glandular Trichomes are modified epidermal hairs and cover leaves, stems & the calyx in the Labiatae. Secretory cells are emanations that are either attached to a stalk or are sessile = attached to a basal cell in the epidermis. We find them in basil Ocimum basilicum, lavender Lavandula spp. Majoram & Origanum spp., mint Mentha spp. & thyme Thymus spp. Also other families contain glandular hairs like hops Lupus humulus in Cannabinaeceae,

source: Secretory structures of aromatic and by KP & TG Svoboda Bastyr Library QK 725.S92.2002 Spices and perfumes – Labiatea or mint family Mints have asymmetric, bilabiate (two-lipped) flowers, often in in axial nodes, square stems and opposite, fragrant leaves (Rosmarinus officinalis), Thyme (Thymus vulgaris) antiseptic; Oregano (Origanum vulgare), Majoram (Origanum sp); Basil (Ocimum basilicum) Chatreuse; Sage (Salvia officinalis) stuffing, (Mentha piperita); spearmint (Mentha spicata)

Picture of leaf glands Secrets of secretory hairs Glandular Trichomes are modified epidermal hairs and cover leaves, stems & the calyx in the Labiatae. Secretory cells are emanations that are either attached to a stalk or are sessile = attached to a basal cell in the epidermis. We find them in basil Ocimum basilicum, lavender Lavandula spp. Majoram & oregano Origanum spp., mint Mentha spp. & thyme Thymus spp. Citrus family Pressurized vacuoles with essential oils protect citrus fruits. Interior of these fruits is isolated by thick cuticle and pectin layer. Secrets of Secretion of Essential oils Secretory cavities are spherical intercellular spaces that are lined with one or more layers of secretory cells. These cavities are found in the peel of Citrus fruits where they appear irregularly as oblate to spherical in the pericarp, in the flavedo (yellow colored part).

source: Secretory structures of aromatic and medicinal plants by KP & TG Svoboda Bastyr Library QK 725.S92.2002 Secrets of Secretion of Essential oils Secretory cavities are spherical intercellular spaces that are lined with one or more layers of secretory cells. These cavities are found in the peel of Citrus fruits where they appear irregularly as oblate to spherical in the pericarp, in the flavedo (yellow colored part). Large secretory cavities are found in the flower buds of cloves Szygium aromaticum, the fruit walls of Pimenta dioica, the bark of myrrh Commiphora, benzoin Styrax and frankincense Boswellia and in the leaves of Eucalyptus spp. source: Secretory structures of aromatic and medicinal plants by KP & TG Svoboda Bastyr Library QK 725.S92.2002 Spices and perfumes – Apiacea or carrot/parsley family

Umbelliferae: umbel as inflorescense; flat-topped clusters of flowers Parsley (Petrosselinum crispum) leaf; dill (Anethum graveolens) leaf; cilantro (Coriandrum sativum) leaf and fruit (coriander spice) Simple Secretory Cells Simple secretory cells occur in the leaf parenchyma of lemongrass Andropogon spp. , bayleaf Laurus nobilis, citronella Cymbopogon spp. & patchouli Pogostemon patchouli, in the seeds of cardamon Eletteria cardamonum, the rhizome of Zingiber offic. & turmeric Curcuma longa & the fruit walls of chillies Capsicum annuum, in the embryo of of nutmeg Myristica fragrans, the bark of cinnamon Cassia angustifolia & Cinnamonum zeylandicum, root of Valeriana offic. source: Secretory structures of aromatic and medicinal plants by KP & TG Svoboda Bastyr Library QK 725.S92.2002 Anatomical signatures Î “Plants have idioblasts” Clear giveaways = signatures = anatomical clues that plants have sequestered lots of active compounds Î (1) glandular trichomes, (2) lacticifers, idioblasts,(3) resin canals, (4) floral & extrafloral nectaries Idioblasts are isolated cells which differ from neighboring plant cells by containing non-living substances. They store starch, excretory materials, pigments and minerals and can contain Ca oxalate raphides emerge from oil, latex, gum, resin, tannin or pigments irritated idioblasts etc. Some can contain mineral crystals such as acrid tasting and poisonous calcium oxalate or silica. Idioblasts are divided into three main categories: excretory, tracheoid and sclerenchymatous. When the end of the idioblast is broken the crystals or other substance is Cross sections of petals of various plants ejected by internal water pressure showing idioblasts around the vascular ring. Secrets of simple Secretion Epidermal cells. Many flowers lack glandular hairs and exude their essential oils from simple epidermal cells through the cuticle to the outside. This primitive mechanism is normally associated with very low yield of essential oils. It occurs in rose petals Rosa spp. , Acacia petals & those of jasmine Jasminum spp.

source: Secretory structures of aromatic and medicinal plants by KP & TG Svoboda Bastyr Library QK 725.S92.2002 Secrets of Secretions Nectar is a sugar-rich liquid produced by plants in glands called nectaries. Nectaries are either within the flowers (Î floral nectaries)., or they are outside (Î extrafloral nectaries). In both cases they provide a nutrient source to animal mutualists. Floral nectaries are located at the bottom of the perianth, forcing pollinators to brush the flower's reproductive structures, the anthers and pistils. Extrafloral nectaries are located on the leaf petioles, mid-rib or leaf margin. Extrafloral nectaries can be found on species belonging to (amongst others) the genera Salix, Prunus (cherries) and Passiflora. Nectar can include other chemicals than sugars. 1. Nicotiana attenuata, a tobacco plant native to Utah, uses volatile benzyl acetone to attract birds but it also adds bitter nicotine to drive the bird away to visit others. 2. Rhododendrons and the California buckeye have neurotoxins such as aesculin & acetyl andromedol that do not harm bees but persist to poison the honey. Anatomical signatures Î f & ef nectaries Clear giveaways = signatures = anatomical clues that plants have sequestered lots of active compounds Î (1) glandular trichomes, (2) lacticifers, idioblasts,(3) resin canals, (4) floral & extrafloral nectaries

Nectar is a sugar- rich liquid in glands called nectaries. They are located either in flowers, or as extrafloral Position of ef nectaries Passion flower with ef varies nectaries, feeding necatries allied animals providing anti- herbivore protection Secrets of simple Secretion Epidermal cells. Many flowers lack glandular hairs and exude their essential oils from simple epidermal cells through the cuticle to the outside. Also buds of a number of species have simple epidermal cells that secrete resinous substances mixed with essential oils that can be used as balsams. This includes Aesculus, alnus, Betula, Populus (cottonwood , Balm of Gilead), Prunus and Rhamnus.

source: Secretory structures of aromatic and medicinal plants by KP & TG Svoboda Bastyr Library QK 725.S92.2002 Secrets of simple Secretions Epidermal cells. Many flowers lack glandular hairs and exude their essential oils from simple epidermal cells through the cuticle to the outside. Also buds of a number of species have simple epidermal cells that secrete resinous substances mixed with essential oils that can be used as balsams. This includes Aesculus, alnus, Betula, Populus (cottonwood , Balm of Gilead), Prunus and Rhamnus.

Poplar Tree Leaf Bud Extract Could Fight Skin Aging ScienceDaily (June 8, 2011) — Antioxidants are popular anti-aging ingredients in skin creams, and now scientists are reporting a new source of these healthful substances -- leaf buds of poplar trees. Their study appears in the ACS' Journal of Agricultural and Food Chemistry. How to make Balm of Gilead salve! Poplar Tree Leaf Bud Extract Could Fight Skin Aging ScienceDaily (June 8, 2011) — Antioxidants are popular anti-aging ingredients in skin creams, and now scientists are reporting a new source of these healthful substances -- leaf buds of poplar trees. Their study appears in the ACS' Journal of Agricultural and Food Chemistry. 1. Collect buds in late winter. Ecological best is to wait until they fall down on their own after the young leaves push them 2. Extract resin by slowly simmering the buds in hot olive or other oil to release their resin, or place buds in a crock, cover them with oil, leaving them to “steep” for weeks or months 3. Make 1:1 ratio of beeswax or myrtle wax shavings and add it to warm (not hot) oil extract. Stir with wooden tool. 4. Some additions could include lanolin, vitamin E oil or coconut oil, all of which slightly change the properties and texture of the salve. Experiment with small batches Secrets of Secretory Ducts Secretory ducts are elongated cavities that branch into networks that often pass between root and shoot. The cavities are lined with secretory cells, where the leucoplast produce the terpenes of the essential oils and secrete them into the cavity.

Another famous example are the resin ducts of in the xylem of the Coniferae reaching 4-10 cm length with 1 to 7 ducts per leaf. Here is the fruit of Juniperus communis Î source: Secretory structures of aromatic and medicinal plants by KP & TG Svoboda Bastyr Library QK 725.S92.2002 Secrets of Secretory Ducts Secretory ducts are elongated cavities that branch into networks that often pass between root and shoot. The cavities are lined with secretory cells, where the leucoplast produce the terpenes of the essential oils and secrete them into the cavity.

Another famous example are the resin ducts of in the xylem of the Coniferae reaching 4-10 cm length with 1 to 7 ducts per leaf.

Here are ducts from needles of Cedrus libanii Î source: Secretory structures of aromatic and medicinal plants by KP & TG Svoboda Bastyr Library QK 725.S92.2002 resin ducts and resin blisters in balsam fir resin ducts are tubes that serve the defense against insects and other animals, which are engulfed by the when boring into the conifer's leaves.. Balsam fir Abies balsamea shows prominent Resin acids are protectants raised blisters full of resin (end of resin ducts) and wood preservatives that Mountain pine beetle drills into pine bark and encounters resin flow, which could kill it.

Resin became amber and pests became jewelry =Î Jurassic Park

Anat. Signatures ÎPlants have resin ducts Clear giveaways = signatures = anatomical clues that plants have sequestered lots of active compounds Î (1) glandular trichomes, (2) lacticifers, idioblasts,(3) resin canals, (4) floral & extrafloral nectaries resin ducts are tubes that serve the defense against insects and other animals, which are engulfed by the Resin canals below the when boring into the hypodermis of pine leaf conifer's leaves.. Resin acids are protectants and wood preservatives that Mountain pine beetle drills into pine are produced by bark and encounters parenchymatous cells that resin flow, which surround the resin ducts could kill it. Poison oak fruit with resin canals. CH Polymers: Resins

Resin is another hydrocarbon secretion of plants, particularly coniferous trees. It is used for production of varnishes, adhesives,; as an important source for incense and perfume. Resins likefrankincense and myrrh originate from ancient Egypt. Some resins are Some resins are soft & known ancient and as 'oleoresins', and when hardened like containing benzoic acid or amber. Amber cinnamic acid they are called often has balsams. Example inclusions of Balm of Gilead is a balm perfectly preserved (healing compound) made from fossil life ( known the resin of the buds of balsam from Jurassic poplar (Populus candicans), a Park). North American tree species. Mastic is the resin of Pistacia trees

Mastic or Masticha is the resin from the Pistacia Lentiscus tree. The trees are commercially cultivated for the purpose of harvesting mastic tears. The very best mastic is said to come from the south side of the Greek Island of Chios. The resin dries on the bark into a Clear, crystalline “tears” which are collected at the end of August,) The teardrops were the first version of chewing gum in Greece. As you masticate, they soften into a firm, chewy mouthful with flavors of licorice and pine. Typically mastic is sold as teardrops although it can also be found as a paste or a powder. The teardrops must usually be ground to a fine powder, usually with sugar, in order to be used for culinary purposes. Resins –purifying incenses of old Mastic is the resin Pistacia lentiscus growing in only a few villages of the island of Chios. Wounded Pistachio trees have resin flow in August. is chewed like chewing gum. Î word masticate, trad. Greece Gum Benzoin is resin produced by the tall Styrax trees (S. benzoin & S. tonkinense) native to Indochina, also called the Java incense trees growing no taller than a person. Gum benzoin was used in Chinese perfumes due to its stable aroma, also in massage oil. The wounded bark fills with yellow fluid that hardens into a reddish mass. Gum guggul myrrh –like resin from the Iranina thorn tree Commiphora mukul, native to western Iran and Eastern India, perfume of Persian women at the time of Alexander’s conquest.. Balsam of Gilead, Balm of Mecca. Resin from 3 m tall trees of Commiphora opobalsamum native to Southern Yemen, kingdom of Saba (queen of Sheba’s gift to Solomon), later planted from Egypt to Palestine, remedy for ringworm + skin diseases. B of Gilead from N. American Populus candicans Î Asafoetida – the ersatz Silphium of Greek antiquity Asafoetida = Europe’s forgotten spice? a repulsively smelling resin from the Iranian Fennel Ferula asa-foetida often adulterated with F. persica & F. galbanum – all tall stout umbellifers The secret of it was first discovered by Engelbert Kaempfer who travelled in Iran & Turkey under cover and wrote 1712 “Five studies ofexotic wonders, political, scientific and medical” Resins –purifying incenses of old Sandalwood: from wood and root of parasitic trees Santalum album, wounding causes gum to flow Î pure native to Indonesia and India. 1000 BC use in India as incense, perfume to enhance sexual attraction (sandalwood resembles male pheromone) and in oil paste applied as UV-protecting sunscreen! Red Sandalwood gives red powder like Santalum but lacks aroma. derived from different trees Pterocarpus santalina that form forests in Madagascar. Decorative wood for pagodas, statues etc. , spice in marzipan & biscuits. Aloeswood resin from tree Aquilaria mallantis native to Eastern has black hard dense wood. Muslim kingdom of Champa (South Vietn) Chinese med. uses it for nervousness, Ayurveda for mental illness. Myrrh reddish-brown resin from dried sap of tree Commiphora myrrha, native to Yemen & Somalia (Punt). Unlike other resins, myrrh expands and "blooms" when burned instead of melting or liquefying .not related to Myrrhis odorata = sweet cicely Flowers to Perfumes Î Labdanum

Labdanum is a sticky brown resin obtained from Cistus creticus the shrubs Cistus ladanifer (western rockrose Mediterranean) and Cistus creticus (eastern Mediterranean), species of rockrose. It has a long history of use in medicine and as a perfume ingredient. In ancient times, resin was scraped from fur of goats and sheep that grazed on the cistus shrubs. The false beards worn by the pharaohs were actually the labdanum soaked hair of these goats. Labdanum is produced today for the perfume industry: The raw resin is usually extracted by boiling the leaves and twigs. The raw gum is a dark brown, rockrose harvest in fragrant mass It resembles Crete ambergris, which has been Discovery of resins as preservatives of meat (volatiles + solids in some resins repel insects, fungi, bacteria) leads Egyptian priests (!!!) to invent ….mummification?? Highly profitable, blame it on Anubis! Queen Hatsepsut and the incense trade with Punt Hatchepsut(Yemen); 1508–1458 BC) was the fifth pharaoh of the eighteenth dynasty of Ancient Egypt & one of the most successful pharaohs, a female

Hatshepsut built a Red Sea fleet to facilitate trade between the head of the Gulf of Aqaba and Punt to bring bitumen, copper, carved amulets, naptha as well as frankincense and myrrh to Karnak in exchange for Nubian gold.

Myrrh or Commiphora Frankincense myrrha tree, releases or olibanum resin upon wounding is a resin from trees of Boswellia, Benzoic acid in perfumes Benzoin resin = styrax resin = benzoin is obtained from the bark of trees in the genus Styrax. Benzoin Sumatra is obtained from Styrax benzoin grown on the island of Sumatra. Both varieties are pathogenic resins, which are exuded from the tree when it is damaged. Its principle component is benzoic acid.

In perfumery, benzoin is used as a fixative, slowing the dispersion of essential oils & other fragrances into the air. It is also used in medicine. Tincture of benzoin has two main medical uses: aseptic treatment for blisters damaged Leukoptape + skin, and as an inhalant in case of bronchitis & asthma. TOB treats blisters on Benzoin resin is important aroma in incensestrips: major comp. of incense of Russian Orthodox Christians also in Japanese incense, Indian incense, Chinese incense, and Papier d'Arménie. Sambrani is a popular Indian incense used to scent hair and prevent infections. Anatomical signatures Î lactifers Clear giveaways = signatures = anatomical clues that plants have sequestered lots of active compounds Î (1) glandular trichomes, (2) lacticifers, idioblasts,(3) resin canals, (4) floral & extrafloral nectaries

Latex is the stable dispersion of natural or synthetic microparticles in an aqueous medium.

Latex is a milky fluid found in 10% Hevea or rubber tree of all flowering plants.

It consists of proteins, alkaloids, starches, sugars, oils, tannins, resins, and gums that coagulates on exposure to air. It is usually exuded after tissue injury. poppies . Cut Euphorbia Euphorbia lathyris or Caper spurge is an erect biennial plant of European origin growing up to 1.5 m tall, with a glaucous blue-green stem and decussate opposite lanceolate leaves. All parts of the plant, including the seeds and roots are poisonous. Handling may cause skin irritation as the plant produces latex. While poisonous to humans and most livestock, goats eat it and are immune to the toxin. However, the toxin can be passed through the goat's milk

This plant is a good source of copious amounts of latex. Since the latex is an emulsion of hydrocarbons in water, this plant was investigated as a possible source of making petroleum. But then the oil prices dropped again and ...da da da Plants and Insects The majority of animals is herbivorous = feeds on plants! Spines, thorns, cuticle, camouflage, repelling smell, taste & deadly toxins are the reason that plants keep dominating (95 %!) the planet’s biomass Herbivores feed only on one to a few plant species because they can only overcome a few of the defense mechanisms. Even humans (only herbi species that cooks & selects population featuresby breeding) feed only on very small number of plants out of the 400 000 species on the planet. E.g. we feed only on the petioles of rhubarb leaves & discard the oxalate-rich blades. H Milky caustic, toxic juice flows through many plants with lactifers (pressurized vessels running in parallel with water- transporting xylem & sugar- transporting phloem). Occurring in Apocynaeceae, Euphorbiaecea, Asteraecea, Caricaceae, Moracea Why do Plants produce a Latex Polymer? 1905 H Kniep carried out classical experiment on chemical defense in plants. By repeated poking the midvein of Euphorbias he drained/milked them & found them now being eaten by snails. Kniep did not know that some insects have practiced his method regularly to avoid being poisoned or muzzled alive!

Drain the lacticifer defense chemicals or suffer the consequences!1 R: Thomas Eisner “ For love of insects” Harvard University Press, 2003 Can Plants produce a Polymer muzzle for Insects? 1905 H Kniep carried out classical experiment on chemical defense in plants. By repeated poking the midvein of Euphorbias he drained/milked them & found them now being eaten by snails. Kniep did not know that some insects have practiced his method regularly to avoid being poisoned or muzzled alive!

Drain the lactifer defense chemicals or get muzzled !!!

R: Thomas Eisner “ For love of insects” Harvard University Press, 2003 Plants help snails to defend against insects! Snails are slow animals, both in the speed of their locomotion & nervous transmission. How do these sitting ducks defend against ants.

When you poke a slug with a toothpick & wiggle it, the slug will produce a rubbery blob around the tip. Ant would be muzzled; fixed mandibles How do snail eggs survive from being eaten? They are protected by an isoprenoid= terpene called miriamine.

R: Thomas Eisner “ For love of insects” Harvard University Press, 2003 Gum-producing plants Chewing Gum The original chewing gum was an invention of native Americans – the Mayans and them Northern tribes. Native American habits easily mislead the innocent White and Black invaders/ newcomers (Indian magic). (1) smoking tobacco (2) chewing tobacco and now (3) chewing gum.

•The ancient Greeks chewed mastiche - a chewing gum made from the resin of the mastic tree. •The ancient Mayans chewed chicle which is the sap from the sapodilla tree. •North American Indians chewed the sap from spruce trees and passed the habit along to the settlers. Olmecs invented games with rubber balls

Visitors to the Amazon describe how Indians coated their feet with latex to be protected from … One of the most mystique nations of Central America were the Olmecs which invented ball games -a most important invention in the history of (wo)mankind. vulcanized latex Rubber in the Americas has been around for centuries. 1. Olmecs invented the rubber ball from latex of Hevea bras. trees. 2. Peruvian Indians made boots by dipping feet in white latex called than “gum elastic” 3. English chemist Joseph Priestley found gum elastic ideal to rub out pencil marks ==> creating the name “rubber” 4. First rubber products suffered from changing temperatures. On hot days it melted & cold days it was hard, brittle & broke. 5. Charles Goodyear mixed latex with anything he could find, e.g cream cheese. 1839 mixing with lime (CaO) + magnesia made latex rubber6. Finally smooth he added & subtle sulfur but to disintegrated. the mix & spilled it over the hot stove. The product lost it stickiness & was not sensitive to temperature. After the god of fire he called it ==> vulcanized rubber. G. remained a pauper. How do plants protect themselves against UV? In the thin air of high mountains, considerably more UV reaches the ground than at sea level. 1. The leaves of many plants contain anthocyanins and flavonols like quercetin as a natural sunscreen = UV filter. 2. Other plants have their leaves covered with dense mats of fluffy hair that reflects most of the UV light. Flavonoids protect plants from UV + us from asthma and hemophilia Quercetin, is found in capers (1800mg/kg), lovage (1700mg/kg), apples (440mg/kg), tea (Camellia sinensis), onion, esp. red onion (higher concentrations in outer rings), red grapes, citrus fruits anti-inflammatory inhibits both manufacture & release of histamine & other allergic mediators. Inhibits mast cell & relieves asthma.

Rutin, is found in buckwheat] , rhubarb Rheum & Ruta graveolens, the common rue. glycoside between the flavonol quercetin + disaccharide rutinose. In humans, it attaches to iron ion Fe2+, preventing it from binding to hydrogen peroxide, Rutin also strengthens the capillaries reduces haemophilia Madder (Rubia tinctorum) Î alizarin red Alizarin is an anthraquinone derived from roots of the madder plant. Most important dye of antiquity: Tut’s cloth had it. 1869 first pigment to be duplicated synthetically. Related dyes: Alizarine Cyanine Green G Alizarine Brilliant Blue R

Madder is the common name of Rubia, a genus of 60 species of perennial climbing native to Old + New world: Common Madder (Rubia tinctorum), Wild Madder (Rubia peregrina), and Indian Madder (Rubia cordifolia). Henna - as natural sunscreen?? Lawsone (2-hydroxy-1,4- naphthoquinone), also known as hennotannic acid, is a red-orange dye present in the leaves of the henna plant (Lawsonia inermis) as well as jewelweed (Impatiens balsamica).. Lawsone can react via Michael addition with the protein keratin in skin and hair, resulting in a strong permanent stain that lasts until the skin or hair is shed. Lawsone strongly absorbs UV light, and aqueous extracts can be effective, sunless tanning sunscreens Chemically, lawsone is similar to juglone, which is found in walnuts. Both are naphtoquinones! Henna (Lawsonia inermis) Henna is a tall shrub/tree, 2–6 m high in family Lythraceae, native to subtropical or semi-arid regions of Africa, southern Asia. Henna repels some insect pests and mildew. In Morocco, wool is dyed and ornamented with henna, as are leather goods. listed in Ebers Papyrus (16th c BCE Egypt) used as hair dye in Indian court ca 400 CE, Henna,produces a red- Henna flowers have been used to create orange dye molecule, perfume since ancient times, lawsone. This molecule has an affinity for bonding with protein, and thus has been used to dye skin, hair, fingernails, leather, silk Tanning Lotions for human skin Tanning oils do not protect from UV but try to enhance its effects. 2 types: (1) Rubefacient indoor tanning lotions containing ingredients that increase blood flow at the skin level and with it more melanin. The ingredients can cause the wearer to experience a tingling sensation (of varying degree). The science is usually accomplished using irritants or chemicals that cause a reddening sensation, flushing the user's skin. (2) Bronzers: Many indoor tanning lotions now contain bronzers, usually dihydroxyacetone (DHA), usually combined with other ingredients to help tanning. DHA is also used in sunless tanning, as the goal is to give the user immediate color. They are often used to jump start the tanning process. Combined with rubefacient ingredients gives them tingle (Hot Bronzers) or cooling agents like menthol to makes them Cool Bronzers. (3) Ingredients: melanin and L-Tyrosine, tea oil, coppercompounds, green tea extract & many other natural oils. Fragrance: a tanning bed is a closed environment, so the aroma of the lotion is important. Moisturizing Tanning dehydrates the skin so that moisturizers are needed. One of the most popular moisturizing elements in tanning lotions is THC-free hempseed oil helping to seal in moisture. Sunscreen Sunscreen (sunblock or suntan lotion) is a lotion, spray, gel that absorbs & reflects the sun's UV radiation to protect the skin.

Sunscreens contain 3 main types : •chemical UV- absorbing compounds such as oxybenzone, suspected photocarcinogen •Inorganic particulates that reflect The market offers few natural & scatter UV light such as sunscreens and yet we know that titanium dioxide, zinc oxide, or a melanins, flavonoids and combination of both naphtoquinones like •Organic particulates that contain lawsone and juglon multiple chromophores and reflect are excellent UV- and scatter light like inorganic absrobing pigments particulates, e.g.Tinosorb M. there is a chance Ingredients of Sunblock Lotions Chemical-free sunblock cocktails contain only Titanium dioxide and Zinc oxide. Others add p-Aminobenzoic acid PABA 15% (5% EC) Titanium dioxide CI77891 25% Zinc oxide 25% (US) 20% (AUS) (EC-Not listed as sunscreen, Homosalate Homomethyl salicylate, HMS 10% (EC, JP) 15% (US,AUS) Octyl salicylate Octyl methoxycinnamate Octinoxate, EMC, 7.5% (US) 10% (EC,AUS) 20% (JP) 1. Benzophenone-3 (Bp-3) 2. Homosalate (HMS) 3. 4-methyl-benzylidene camphor (4-MBC) 4. Octyl-methoxycinnamate (OMC) 5. Octyl-dimethyl-PABA (OD-PABA) 6. Parabens 7. Butyl-methoxydibenzoylmethane (B-MDM) The first six of these chemicals, found in sunscreens of every type, were found to be estrogenic, whereas the seventh was inactive. Xenoestrogens are non- steroidal compounds that bind to the estrogen receptors (endocrine disrupters), which can cause reproductive problems. Sunblock Lotions First sunblock solution was used by the ancient Egyptians who rubbed castor oil on their bodies. The first effective sunscreen was developed by chemist in 1938 Franz Greiter called Gletscher Crème (Glacier Cream),

Greiter introduced Sun Protection Factor (SPF) in 1962 The SPF of a sunscreen measures the effectiveness of sunscreen — the higher the SPF, the more protection a sunscreen offers against UV-B = the ultraviolet radiation that causes sunburn. The SPF is the time extension factor of a sunscreen to prevent sunburn relative to a person without it.

Example: someone who burns after 12 min in the sun would be expected to burn after 120 minutes if protected by a sunscreen with SPF 10. Protection against the sun’s UV Sunscreen is to protect the skin against UV = 280 to 400 nm reach the earth surface (other UV-C is 200 –280 nm is absorbed by molecular oxygen in the ozone layer). Left for us is UV-B is 280 –320 nm, UV-A is 320-400 nm. UV-B has short penetration into the upper dermis and its absorption (by DNA and other blue-light absorbing pigments + melanin) causes redness or sunburn & later the generation of melanin from tyrosine in the dermis (max effect at 305 nm

UV-A penetrates deeper into the dermis where it damages connective tissue (skin damage) & via free radicles causes tumor. Allergic photosensitivity is caused by UV-A, creates no erythema only transient tan.

Since UV-A causes little erythema it is used in tanning salons. Whether the tan protects against UV-B is unknown. You risk melanoma

Max exposure from 9 – 3 PM, near the equator & at high altitudes. Protection against the sun’s UV Sensitivity against UV depends on the level of melanins in the dermis – the natural protection of animals and a factor of racial difference (skin type classification I (burns easy) to VI (neverIn USA burns)sunscreens are OTC (over-the-counter) drugs or cosmetics. Sunscreen contains a number of of UV-reflecting or UV absorbing substances (Titanium dioxide is broad-band UV blocker, benzephones are UV-A absorbers) together with moisturizingSPF or sun protection oils. factor measured by skin redness. If a person develops redness after 20 min exposure and with sunscreen after 80 min , the SPF is 4.

Burn-blocking waxy stick formulation: for nose ears, lips Zinc oxide or Titanium dioxide 10%, Petrolatum 74 % (Wt) Paraffin wax 16 %, add Color & fragrance Tattooing – an ancient art Traditional tattooing involves the breaking of the skin stick and poke" is keeping tip of a sewing needle saturated with ink, the skin is pricked over and over, creating a design. Risk of infection and the permanence of a tattoo that may be later embarrassing. The use of mostly Henna,produces a synthetic tar dyes – and yes this includes carbon red-orange dye black – another concern. molecule, lawsone. This molecule has an affinity for bonding with protein in the epidermis and does not need the implantation into deeper layers. Natural Plant Insecticides - Repellents Plants produce many powerful insecticides like nicotine (Nicotiana plants), plant sterols (drug precursors), urushiol (poison oak and ivy oil), as well as pyrethrum, chrysanthemic acid and rotenone (insecticides) andIn addition neem plants oil. produce essential oils are peppermint oil, clove oil, citrus oils, lavender oil, thyme oil, and rosemary oil as insect repellents essential oils that work well against biting insects: cinnamon oil (mosquitoes) castor oil (mosquitoes) eucalyptus oil (mosquitoes, ticks, and lice) citronella oil (mosquitoes and biting flies) orange oil (fleas) rose geranium (ticks and lice) Safe carrier oils and alcohols include: olive oil, sunflower oil, other cooking oil, witch hazel, vodka good rule of thumb is to mix the repellent so it's 5-10% essential oil, so mix 1 part essential oil with 10-20 parts carrier oil Natural Plant Insecticides - Pyrethrum Pyrethrum refers to plants of the genus Chrysanthemum which are cultivated as ornamentals. It is the name of a natural insecticide made from the dried flower heads of C. cinerariifolium and C. coccineum. Pyrethrum was used for centuries as an insecticide & as a lice remedy ("Persian Insect Powder)

The flowers are pulverized and pyrethrins, contained in the seed cases, are extracted in the form of an oleoresin. Applied as a suspension in water or oil, or as a powder, pyrethrins attack the nervous systems of all insects, and inhibit female mosquitoes from biting.

Pyrethroids are synthetic chemicals similar to the natural chemical pyrethrins produced by the flowers of pyrethrums (Chrysanthemum cinerariaefolium and C. coccineum). They are a major part of the insecticide market and common in household insecticides.

Pyrethroids are able to pass through secondary treatment systems at wastewater treatment facilities in levels lethal to invertebrates. Insecticides from the Neem tree = Indian lilac Neem tree inhibits development of insect larvae but is harmless to mammals (us), bees and ladybugs. The chemical compound responsible for Neem action is azadirachtin = an unusual tetra-terpenopid

Neem (Azadirachta indica) is an evergreen tree in the mahogany family Meliaceae. It is one of two species in the genus Azadirachta, and is native to Indian subcontinebt plus East Africa: Mwarobaini (Swahili), which means the tree of the 40; it's said to treat 40 different diseases. Natural Plant Insecticides – Neem oil Neem oil is pressed from the fruits and seeds of neem (Azadirachta indica), an evergreen tree from India. Used for org farming & medicine Neem oil is brown, bitter with strong odour that combines peanut and garlic. It consists of triglycerides and large amounts of triterpenoids, which give it the bitter taste. Azadirachtin is the most well known and studied triterpenoid. Another triterpenoid isolated from neem is salannin -a powerfull insect repellent, Active as feeding inhibitor against the desert locust (Schistocerca), it is now known to affect > 200 species of insect, by acting mainly as an antifeedant and growth disruptor, with high toxicity toward insects (LD50(S. littoralis): 15 ug/g). Azadirachtin is biodegradable (it degrades within 100 hours when exposed to light and water) & has very low toxicity to mammals (the LD50 in rats is > 3,540 mg/kg = non-toxic).

Azadirachtin is structurally similar to insect hormones called "ecdysones," which control metamorphosis of insects passing from larva to pupa to adult. Natural Plant Insecticides – Rotenone Rotenone is an odorless flavone molecule that is used as a broad- spectrum insecticide, piscicide, and pesticide. It occurs naturally in the roots and stems of several plants such as: Florida fishpoison tree (Piscidia piscipula) – southern Florida, Jicama vine plant (Tephrosia virginiana) – North America Cubé Plant or Lancepod (Lonchocarpus utilis) – South America Jewel Vine (Derris involuta) – SE Asia & SW Pacific islands the

Rotenone is badly taken up by skin and human guts but well by gills of fishes Î fish poison, used by Amazonians to fish & today to stop invasion of invading fish species in access streams. It interferes with the electron transport chain in mitochondria.

Rotenone is the most effective tool available because it has only minor and transient environmental side-effects.