Phytochem class 7.pdf

Class 7 • Phenols • What are phenols? • Any compound with a hydroxyl group (OH) directly linked to a benzene ring • What is a benzene ring? • They are characterized by a ring of 6 C atoms, bonded together by alternating single and double bonds • Vanillin • • • • • Phenol Synthesis • How are they...

Class 7 • Phenols • What are phenols? • Any compound with a hydroxyl group (OH) directly linked to a benzene ring • What is a benzene ring? • They are characterized by a ring of 6 C atoms, bonded together by alternating single and double bonds • Vanillin • • • • • Phenol Synthesis • How are they produced? • They are built from the amino acid phenylalanine • This amino acid is produced via the…. • Shikimic acid pathway • Are all phenols produced this way? • No, in fact • Some phenols + flavonoids & tannins are actually created from acetyl-CoA What is this? • • A phenol Where can it be found? • In most plants, actually, typically in very small amounts • Vanilla leaf also produces this compound Difference in flavour • Vanilla extract consists primarily of vanillin but ALSO other compounds that create a well rounded profile • Artificially this will taste similar but different, as it is pure vanillin that is dissolved in ethanol without the rest of the entourage How is vanillin produced commercially? • It is made by wood that is broken down into much smaller pieces • A small amount can be produced from lignin (found mostly between plant cells and within cell walls = fiber) • This is a waste product of the wood pulp industry Actions • Acts as an insect repellant for mosquitos • Antifeedant for herbivorous insects • Coumarin Class 7 • Salicylic acid • What type of compound is this in a plant? • A primary and secondary metabolite • Roles • A hormone, primary, used to assist with growth and development but centrally to defend the plant from infection • As a secondary metabolite • It helps to prepare a plant to resist an attack • This can be modified into a volatile substance, to communicate with other plants when dispersed into the air, acts as a signal/alert • Irritant, as it disrupts membrane integrity (breaks things down) • Ethnobotanical use • Anti-inflammatory and anti-pyretic • Herbal medicine and Pharmaceutical use • Performs the actions mentioned above by inhibiting COX-1 and COX-2 enzymes • They are responsible for producing prostaglandins • Molecules responsible for inflammation, fever, and pain • As this plant act as an irritant to other animals we are then also included in this case • Short-term minor irritation of the GIT may occur • Long-term use may lead to ulceration of the GIT • These are compounds that are released by plants after being cut • Such as hay having a sweet smell + clover and cherry blossoms produce this scent while flowering • Rest of their flavour profile • They do contain a bitter flavour that acts to deter most organisms from consuming them • N.B. • When consumed this molecule exhibits an appetite suppressing action • The plant essentially says thar “you are now full” • Warfarin • What is this? • Anticoagulant • How is it related to this topic? • The chemical structure is based off of a modified coumarin • Discovered in moldy sweet clover that made a herd of cattle sick in the 1920s • This series of events led to the discovery of an isolate that became coumadin = warfarin in the 1940s • How is it acting in the body? • Competitively inhibits the vitamin K recycling process • As a result, this is able to deplete reserves and thereby reduces the production of active clotting factors • Is this used with any other species? • Yes, it is used with rodents as a rodenticide • It is significantly more toxic, as they are unable to vomit Class 7 • Furanocoumarins • What are they? • They are a group of secondary metabolites that commonly present in higher plants, such as citrus’ • Where can they be found? • In plants i.e., celery and other related species, and citrus • What types of effects do they have on animals? • Many of these compounds are toxic and can produce a very painful and itchy rash that can last upwards of 10 days • They cause phytophotodermatitis, by an action as simple as touch for a few moments • Many of them are photoreactive • How do they perform this action? • By reacting with nucleobases in DNA under the influence of UV-A radiation • Subsequent exposure to this radiation leads to cross-links which develop in DNA • DNA lesions, damage, are then produced in cells • Bergamottin • What is this? • This is a furanocoumarin • It is not UV sensitive but is still quite reactive • Where can it be found? • Bergamot, grapefruit, orange, and pomelo • The highest concentration is present within grapefruit • Cytochrome • Cytochrome P-450 (CYP450) enzymes in the liver are involved in the metabolism (major detox pathway) of chemicals, drugs, and endogenous substrates. • They are also involved in the pathogenesis of various liver diseases • When certain substances pass through CYP450 they can end up becoming hepatotoxic i.e., acetaminophen Class 7 • Bergamottin • What effect does bergamottin have on a human? • It acts as a irreversible inhibitor of cytochrome P450 • Now, for the next 72 hours drug concentrations will become increased, so long as they are processed by this enzyme group • The effects are strongest 4 hours following assimilation • 24 hours following assimilation the enzymes then regained half of their initial capacity • Where was this affect first noticed? • Within the elderly population • Psoralen • What is this? • • Where can it be found? • • • A furanocoumarin Celery, citrus, figs, parsley, St. John's Wort What type of action does it exert? • Phytophotosensitivity • This action is achieved by inserting itself within helixes of DNA, which interferes with DNA i.e., new copies, transcription, proteins, etc. This is in fact a mutagen Why do we have standardized psoralen products? • This has a variety of effects i.e. • PUVA treatment for eczema, psoriasis, certain forms of lymphoma, and vitiligo • Tanning agent • Skin whitening product • You are much more likely to experience SUNBURN Class 7 • Lignans • These are phenolic compounds • What roles do they serve? • Dietary lignans, in humans – are associated with a reduced risk of developing cardiovascular disease • Hormone mimics - defensive • Toxic compounds – defensive • N.B.– different from lignin (where vanillin is extracted from) • Lariciresinol • Where is this found? • Found in sesame seeds, brassica vegetables, and bark and wood of white fir • This is a lignan • What types of actions does this posses? • In plants, it acts as an antifungal, to minimize chances of developing an infection • In humans, • High dietary consumption has been noted to reduced the risk of developing breast cancer • This compound interacts with gut microflora to produce enterolignans which are much stronger anti-cancerous compounds than lignans alone • Podophyllotoxin • What is this? • A lignan • Where can it be found? • Within Mayapple’s • What roles does this serve? • Inhibits an enzyme involved in the duplication of DNA, anti-cancerous activity • Due to this activity it is currently used as treatment for general and genital warts in Europe, anti-viral activity • This compound is continually being studied as a anticancerous agent • Etoposide and teniposide are semi-synthetic derivatives of this compound Class 7 • Lignin • Flavonoids • Wood is comprised of lignin • It plays a very important role when it comes to structure, hydrophobic properties, and transportation of minerals throughout the vasculature of a tree • What are they? • They are a large group of phenolic compounds with various subgroups • While this component is widely used amongst plants worldwide it is organized slightly differently from species to species and even individual to individual • Distribution may be different i.e., base, middle region, or top of the tree • Where can they be found? • While they can be found in nearly all plants they are in higher concentrations of cocoa, black tea, wine, citrus, blueberries, etc. • Carbon cycle • This is one way to store carbon long-term through a process called ________ • Limitation of this compound • Lignin is difficult to work with therefore it slows down the production of pulp and paper mills • GMO projects have been undertaken to develop trees with less or modified forms of lignin to allow for easier processing • What sort of roles do they play? • They are noted to be rich in antioxidants, offer defensive and communication molecules, and can offer some UV protective capacity • Are they toxic? • They are incredibly safe for humans to consume • We can have LARGE amounts before experiencing any difficulties Class 7 • Assimilation of Flavonoids • How efficient is this process? • Between 2-5% of flavonoids are actually absorbed • The rest are broken down rather rapidly once introduced to the stomach • What waste product do they generate within the GIT? • Uric acid • This is suspected to exert antioxidant activity • How long would they last in one’s system? • Around 2 hours maximum • As a result, from a western based perspective, their usefulness is questioned as therapeutic agents • Phytoestrogens • Recall • Estrogen is a triterpene; humans begin with a 30 C chain and then cleave 3 C off to produce cholesterol which is then utilized to produce a steroid hormone • Phytoestrogens are typically classified as flavonoids, lignans, or other phenols • These compounds are only attempting to cause an effect if and when they are consumed • Once consumed they are attempting to disrupt signalling within the predator • It directly interferes with the reproductive and metabolic pathways of those animals • Biology • Humans have 2 estrogen receptors: alpha and beta • Estrogen will naturally bind to both • Phytoestrogens • Do not bind to both receptors • They will tend to have an affinity for beta-receptors • As a result, this is not classified as a perfect mimic but rather imperfect • Due to this these compounds do not exert as profound of an action as animal based or synthetic estrogen • Plants that contain phytoestrogens • Red clover (Trifolium pretense) • Soy (Glycine max) Class 7 • Rotenone • Rhizobium • What is this? • A flavonoid • What are these? • They’re bacteria that live in small nodules found on roots • Where can it be found? • Within the leaves of a jicama plant along with the genus’ Derris, Lonchocarpus, or Tephrosia • Where can they be found? • These bacteria can be found living on the roots of pulses (beans, peas, and lentils) • How has this compound been used? • Ethnobotanically it has been used to by people of Central and South America to catch fish, piscicide • Effectively as an insecticide • What is the purpose of this relationship? • Bacteria receives food in the form of sugar and a space to live • Plant receives N that is fixed into the soil • How does it perform such a profound activity? • This inhibits the transfer of electrons in the ETC from proteins 1 to 2 • It therefore inhibits O2 transfer and cellular respiration • Can this impact land animals? • How can the plants pick the appropriate species? • They have checks and balances to begin with • Plants use flavonoids to communicate with the rhizobia bacteria • Bacteria use chemicals to communicate with the pulses • It has a less profound effect on terrestrial creatures but can still profoundly impact a human being by causing nausea, vomiting, • , Class 7 • Anthocyanins • What are these? • They are a type of flavonoid • Where can we find them? • They are typically seen as pigments (pink, red, purple, blue) best used as attractants in flowers and as UV protective agents in leaves • Are they similar to carotenoids? • Yes, in regard to the fact that they both produce pigments to protect leaves from excessive light damage • No, in regard to the fact that anthocyanins are water soluble and carotenoids are not • What types of stimuli bring about their production? • They may be increased due to stressors i.e., heat, pH, high salt content, low nutrients, etc. • Relationship of some anthocyanins • Most of these flavonoids contain very similar chemical structures • Subtle changes can end up drastically altering things • Swapping one molecule of O for H or one H for C can produce a dramatic colour change • In this circumstance, changes on the microscopic scale can end up generating a dramatic alteration in the macroscopic world • What types of therapeutic effects do they have for humans? • Antidiabetic • Anticancer • Anti-inflammatory • Antimicrobial • Cardioprotective • What holds back their therapeutic potential? They have a VERY low stability and can be affected by things i.e., humidity, light, pH, temperature, sugars, vitamin C, etc.