PHARMACOGNOSY AND PLANT CHEMISTRY
REVIEWHoneylene B. Paloma, RPh.
Pharmacognosy
• Principally concerned with plant materials however, there are small number of animal products w/c are traditionally encompassed within the subject;
• Examples– Produced from wild (whale, musk, deer)– Fish (cod and halibut)– Domesticated animals (hog, sheep, cattle) –
lanolin, milk products, hormones, endocrine products and some enzymes
– Wild insects (cantharides)– Cultivated (beeswax)
• Marine organisms, both plant and animal, with potent pharmacological actions are receiving increasing attention in the search for new drugs
Pharmacognosy
• Drugs from natural sources
• Study of drugs from natural sources– Plants– Animals– microbes
Pharmakon GnosisDrugs Knowledge
Pharmacognosy
• Materials having no pharmacological action which of interest to pharmacognosists are natural fibers, flavoring and suspending agents, colorants, disintegrants, stabilizers and filtering and support media
• Other areas that have natural associations with the subject are poisonous and hallucinogenic plants, allergens, herbicides, insecticides and molluscicides
Pharmacognosy
• The study of drugs used by traditional healers is an important object of pharmacognostical research
It may be defined as an important branch of Pharmacy which deals with the study of structural, physical, chemical, biochemical and sensory characters of natural drugs of plant and animal origin. It also includes a study of their history, distribution, cultivation, collection, identification, preparation, evaluation, preservation, use and commerce.
Pharmacognosy - History
• The first or beginning of pre-history on use of medicinal plants or herbs or animals, and the place where and how used were not well known, and those information were unwritten for a long time. As a result, the pre-history on herbs was almost lost.
• However, some information was recorded by oral transmission from generation to generation.
Pre-history:
History of pharmacognosy is actually the history of medicine that is medicinal plants.
Pharmacognosy - History
• The written history has originated which was based on region, religion and culture etc.
The written history was divided into the following:
1. The western medicine2. The Unani (Islam)3. The Ayurveda (Indian)4. The orient5. The Greek History6. The African System7. The European exploration
Written History:
Pharmacognosy - History
This is originated in Mesopotamia and Egypt. Mesopotamia is considered as the first origin of human civilization. The Sumerians (peoples of ancient Mesopotamia) developed cuneiform tablet of herbal medicines. Those tablets is preserved in British museum.
In Egypt, information had written on paper – Papyrus ebers (1550BC). It consisted of 800 prescriptions, mentioning 700 drugs.
The first pharmacopoeia named London Pharmacopoeia was published in 1618 and then British Pharmacopoeia was published in 1864.
1. The western medicine:
HISTORY - SUMERIANS AND AKKADIANS (3RD MILLENNIUM BC)
HISTORY – Egyptians (Ebers papyrus, 1550 BC)
• This herbal system was developed by Arabian Muslim Ibn Sina (980 – 1037 AD). He was a prince and ruler. He was a very brilliant pharmacist and physician who wrote a book – “Kitab-Al-Shifa”, means ‘Book of Healing’.
• The book was written on Arabic language. This is a great contribution of Ibn Sina on medical and pharmaceutical sciences.
Pharmacognosy - History
2. The Unani (Islam)
The Islamic era Ibn Altabari (770850) ” الحكمه “فردوس
Ibn Sina (980-1037) ” الطب في “القانون
Ibn Albitar (1148-1197)” واألغذية األدوية لمفردات “الجامع
Ayurveda is the term for traditional medicine of ancient India. The word “Ayur” means ‘Life’ and “veda” means ‘The study of’ that is “Study of Life”.
The Ayurvedic writings were divided into three systems:
1) Charaka Samhita, 2) Sushruta Samhita and 3) Astanga samhita.
The oldest writing was Charaka Samhita (six to seven century before Christ).The book describes uses of many metallic drugs eg., iron, mercury, sulphur, cupper etc with herbs.
3. The Ayurveda (Indian, 2500-600 BC):
HISTORY
This is originated from Chinese, Japanese and Tibet etc. The orient herbalism was very old (142 – 220 BC) and called “Kampo”. The written documents were made by the King ‘Shen Nung’ (2700 BC) and Shang (1766 – 1122 BC) etc.
Shen Nung investigated medicinal value of several herbs and written a book – “Pen T-Sao” or native herbal.
4. The orient (2700 BC):
Hippocrates (Father of Medicine, 460-370 BC): He was the first natural doctor who utilized simple remedies such as vinegar, honey, herbs etc in healing. He is also known to have collected and identified a number of medicinal plants.
Aristotle (384-322 BC): He gave the philosophy of medicine. He listed more than 500 plants of medicinal importance.
Theophrastus (340 BC): Father of Botanygave scientific basis of use of plants as medicine.
Galen (131-200 AD): a Greek pharmacist-physician. He developed the methods of preparing and compounding medicines by mechanical means. He was the originator of the formulae for a cold cream.
5. The Greek History:
Authors of antiquityHippocrates (460-370 BC)
“The Father of Medicine”
Dioscorides (40-80 AD)“De Materia Medica” (600 medicinal plants)
HISTORY• Greeks
–Pedanius Dioscorides• Wrote the book De Materia Medica
• Father of Pharmacology–Aloe Ergot–Colchicum Opium–Belladonna
HISTORY• Greeks
–Claudius Galen• Father of
Pharmaceutical Compounding
• Prepared formula of drugs containing plant and animal constituents
• Galen’s Cerate
They keep information in their groups or tribes. The information transmitted from one generation to another.
These regions are richest sources of medicinal plants and needs to explore for new drug discovery.
6. The African System (Tropical Africa, North and South America):
7. The era of European exploration overseas (16th and 17th century)
HISTORY• Germans
–C.A. Seydler coined the term pharmacognosy
– J.A. Schmidt wrote Lehrbuck de Materia Medica
–F.A. Fluckiger described the most comprehensive scope of pharmacognosy
The 18th century, Pharmacognosy• Johann Adam (1759-1809)
• Linnaeus (naming and classifying plants)
• At the end of the 18th century, crude drugs were still being used as powders, simple extracts, or tinctures
The era of pure compounds(In 1803, a new era in the history of medicine)• Isolation of morphine from
opium
• Strychnine (1817)
• Quinine and caffeine (1820)
• Nicotine (1828)
• Atropine (1833)
• Cocaine (1855)
HISTORY– F.A. Fluckiger described the most
comprehensive scope of pharmacognosy• Scope:
– Biologic a pharmacognosist should be familiar with the biologic sources of the drug
*Father of Taxonomy Carolus Linnaeus- Economic- Biochemical
- Constituents:Pharmaceutically activePharmacologically active
Historical Milestones of TradMed in the Philippines
• Spanish Period - Earliest document is an
unpublished treatise on indigenous medicinal pants written by a Franciscan around 1611
- Fr. Blanco’s Flora de Filipinas (1737, 1845,1877)
- Dr. Pardo de Tavera’s Plantas Medicinales de Filipinas (1892)
Historical Milestones of TradMed in the Philippines
Percent of Children with Mothers receiving two or more doses of TTV during pregnancy has been decreasing, from 42.2 percent in 1993 to 32 percent in 2002. One reason for the decline is the campaign of the Catholic Church against Tetanus Toxoid in 1995.
Historical Milestones of TradMed in the Philippines
• American Period - characterized by
scientific vigor - establishment of the Government
Laboratories (Bureau of Science)
- intensive research on chemical constituents, pharmacology and therapeutics of medicinal plants by
UP
Historical Milestones of TradMed in the Philippines
• Commonwealth Period - extension of surveys to
regions not previously explored- clinical and chemical
investigations were made though in a limited scale
Historical Milestones of TradMed in the Philippines
• Japanese Occupation- Impetus given to the
cultivation of medicinal plants
- E.O. 14 creating a committee on medicinal plants for the purpose of local production and manufacture of medicines from herbs
Historical Milestones of TradMed in the Philippines
• Immediate Post World War II Period
- First major exhaustive work on medicinal plants by a Filipino - Quisumbing’s Medicinal Plants of
the Philippines, 1951
Historical Milestones of TradMed in the Philippines
• Contemporary Period (1970 – present)
- establishment of Community-Based Health Programs (CBHPs) in the early 70s which promoted the use of indigenous knowledge and resources for primary health care
- creation of the National Integrated Research Program on Medicinal Plants (NIRPROMP) in 1977
Historical Milestones of TradMed in the Philippines
Technology transfer from NIRPROMP to the private sector for the production of 7 herbs into commercial formCreation of TradMed Unit at DOH in 1992RA 8423 creating the Philippine Institute of Traditional and Alternative Health Care (PITAHC) Inclusion of survey questions towards TradMed in the 1998 and 2003 National Demographic and Health Surveys of NSO
SURVEY OF LITERATURE
A. Socio-Cultural Aspects of Indigenous Medicine 1. F.L. Jocano’s Folk Medicine in a Philippine Municipality (1973)
- an ethnographic account of folk medicine among peasants in Bay, Laguna 2. M. L.Tan’s Usog, Kulam, Pasma (1987)
- formulated theoretical typologies of illness causation based on the literature
SURVEY OF LITERATURE: Socio-Cultural Aspects of Indigenous Medicine
3. Department of Health (DOH)-Community Medicine Foundation (COMMED), Filipino Traditional Medicine Comprehensive Database Project, 1995
- included an annotated bibliography consisting of ethnographic, historical and pharmacological literatures
- derived six major themes in traditional medicine in the Philippines based on literature and results of the mapping of 191 TradMed practitioners, their demographics, healing practices and philosophy, as well as their distribution and networking
SURVEY OF LITERATURE: Socio-Cultural Aspects of Indigenous Medicine
4. Isidro Sia and NIH Study Group Documentation of 15 Ethnolinguistic Groups and their Traditional Medicine Practices - focused on 15 ethnolinguistic groups in the Cordilleras, Palawan, other parts of Luzon, and Mindanao
SURVEY OF LITERATURE: Socio-Cultural Aspects of Indigenous Medicine
5. Int’l. Institute of Rural Reconstruction (IIRR), Indigenous Knowledge and Practices on Mother and Child Care: Experiences from Southeast Asia and China (2000)
- contains extensive discussions of maternal and child care in different cultural settings in the Philippines as well as other parts of Asia
- chapter on retrieval, documentation and use of IK, with most of the cases based on community level initiatives in the Philippines
SURVEY OF LITERATURE: Socio-Cultural Aspects of Indigenous Medicine
6. Planta’s master’s thesis on the development of traditional medicine and pharmacopoeia in the 16th to the 19th centuries (1999)
- attempts to portray Filipino culture and society through its traditional medical and healing practices
SURVEY OF LITERATURE – Medicinal Plants Inventory
B. Medicinal Plants Inventory
1. E. Quisumbing’s Medicinal Plants of the Philippines, 1951
- regarded as one of the earliest and most authoritative texts on medicinal plants
2. UP Botanical Society’s Manual on Some Philippine Medicinal Plants (1977)
- sought to enlighten people of the potential healing properties of local medicinal plants, with sections divided according to medicinal properties of plants
SURVEY OF LITERATURE – Medicinal Plants Inventory
2. M. L. Tan’s Philippine Medicinal Plants in Common Use: Their Phytochemistry and Pharmacology (1977)
- discusssed more than 200 plants; each plant entry is accompanied by its scientific and local name, a brief description of the plant and suggested preparations and uses
SURVEY OF LITERATURE – Medicinal Plants Inventory
3. Leonardo Co’s Common Medicinal Plants of the Cordillera Region (1984)
- covers 122 species of common medicinal plants found in the Cordillera region
4. Quintana’s Philippine Medicinal Plant: Abstract and Bibliography (1989)
- collated and organized references on medicinal plants resources from the UPLB campus’ libraries as well as other private I libraries
SURVEY OF LITERATURE – Medicinal Plants Inventory
5. Ludivina de Padua’s Medicinal Plants (1996)
- conceived to be a series of several booklets that “approaches plant science from the ecological perspective rather than purely taxonomic”
SURVEY OF LITERATURE – Pharmacological Studies of Philippine Medicinal Plants
1. Jaime Zaguirre’s Some Emergency Bedside Preparations of Most Common Local Medicinal Plants (1955)
- written in 1944 and re-circulated in 1949 primarily among the Medical Field Service of the AFP
2. Dr. Jocelyn Cruz, Herbal Medicine-A Viable Alternative for the Filipino People (1985)
- documents early pharmacologic tests undertaken by Dr. Alfredo C. Santos in 1927
3. NIRPROMP-led pharmacologic research
- documentation of rapid screening process to study the efficacy and safety of medicinal plants, then the agricultural, pharmaceutical and clinical trials of plants that have passed initial screening
4. Departments of Pharmacology of the University of the East and UP Manila, Pharmacologic studies done by students
SURVEY OF LITERATURE – Pharmacological Studies of Philippine Medicinal Plants
4. PCHRD-HERDIN bibliographic database of health literature in the Philippines - includes 2,000 records on traditional medicine comprising mainly of journal articles, research reports, paper and conference proceedings
SURVEY OF LITERATURE – Pharmacological Studies of Philippine Medicinal Plants
1. Segismundo’s Filipino Traditional Medicine and the Development of a Relevant Health Care System (1994)
- critiqued the weaknesses of the health care system and cited efforts through NGOs and the CBHPs for the integration of TradMed
2. Castro-Palaganas, et. al., Mainstreaming Indegenous Health Knowledge and Practices (2001)
- specific focus on indigenous notions of health or kasalun-alan and the women’s life cycle
SURVEY OF LITERATURE – Mainstreaming Traditional Medicine
SURVEY OF LITERATURE – Mainstreaming Traditional Medicine
3. M. L. Tan’s Traditional Medical Practitioners (1992)
- showed the different types of traditional medical practitioners, their socio-geographic characteristics, skills acquisition, methods of diagnosis and healing
4. NSO’s National Demographic and Health Surveys (1998, 2003)
- included questions on the knowledge, attitude and practices of Filipinos towards traditional medicine
SURVEY OF LITERATURE – Mainstreaming Traditional Medicine
5. Various handbooks on medicinal plants produced by government, NGOs and academic institutions
- information on medicinal plants and their therapeutic uses aimed at re- educating health workers, trainors and community members
Plants are grouped into about 383 families (Woodland 2000). Members of the same family are similar. Thus, apples, pears and roses are in the same family (Rose Family, Rosaceae), crabgrass, Kentucky bluegrass and seagrasses are in the same family (Grass Family, Poaceae) and sunflowers, asters and calendulas are all in another family (Sunflower Family, Asteraceae).
All plant families are based on the name of one genus in the family, with –ceae added to the stem. Aster Asteraceae, Juglans Juglandaceae; Lilium Liliaceae;Malva Malvaceae; Orchis Orchidaceae; Rosa Rosaceae; Salix Salicaceae… etc… 383 families…
EXCEPT
There was a system before this system was imposed (International Code of Botanical Nomenclature Article 18). The family names of the biggest most common plant families in the old system were in such wide use that there was a battle among the delegates at the International Botanic Congress over whether ALL families had to conform to the new system. The reformists did not win, they compromised. For 6 big families BOTH the new name or the traditional name are EQUALLY acceptable. Thus
Ehretia microphylla
Scientific Name: Mentha cordifolia / Clindopodium douglasii
Formation of ConstituentsBiogenesis or Plant
BiosynthesisPrimary Metabolites
Secondary Metabolites
Carbohydrates Glycosides, Gums and Metabolites
Fats Fixed oil, fats, waxes, and volatile oils
Proteins AlkaloidsAffected by: (OHE)1. Ontogeny or the Stage of Development2. Heredity3. Environment
Formation of Constituents:Other Examples:
1. Codeine – Pierre Robiquet2. Morphine – Friedrich Serturner
• Named after the Greek God of Sleep Morpheus3. Quinine – Pelletier and Caventou
Crude Drugs• Drugs that are collected and
dried.• Undergone only the process
of collection and drying.
Ethnobotany• It is a broad term referring
to the study of plants by humans
Ethnomedicine• It refers to the use of plants
by humans as medicine
TradMed – Traditional Medicine
• It is the sum total of all non-mainstream medical practices, usually excluding so called “western” medicine
Crude Extract• Mixture of constituents
isolated from Crude Drugs.
NAME THE 7 WAYS ON HOW TO PREPARE CRUDE DRUGS IN THE
MARKET?
Preparation of Crude Drugs
1. Collection (in small scale)- To ensure the true natural
source of the drugs- Collection time to isolate the
right type and right amount of constituents
Examples:Digitalis lanata – white flowerDigitalis purpurea – purple flowerProtopectin – unripe fruitsPectin – for just ripe fruitsPectic acid – for over riped fruits
2. Harvesting (in large scale)- maybe mechanical or manual
*if the drug collected is potent manual harvesting
3. Drying – to ensure good keeping qualities
4. Garbling – the final step in the preparation of crude drugs; sorting; removal of extraneous portion
Preparation of Crude Drugs
5. Packaging6. Storage
- to prevent insect attacka. simplest methodb. fumigationc. add a drop of preservative
7. Preservation
Preparation of Crude Drugs
Methods of Extraction1. Percolation
MenstruumMarcPercolate
Substance Menstruum
Fats
Resins
Chlorophyll
Solanine
Chrysarobin
HexaneEthanolAcetone
Acetic AcidHot Benzene
Hexane
Ethanol Acetone
Acetic Acid
Hot Benzene
Methods of Extraction2. Maceration – solid
ingredient are placed in a stoppered container with the prescribed menstruum and allowed to stand for a period of 2 – 3 days in a warm place with frequent agitation, until soluble matter is dissolved.
Methods of Extraction3. Infusion – macerate solids
for a period of time in either hot or cold water.
4. Decoction – drugs are subjected to boiling in water for 5 – 10 mins; cooling, straining, and passing sufficient cold water through the drug.
Indigenous vs Naturalized Plants
– plants growing in their native countries
Aloe barbadensisPrunus armeniacaAcacia senegal
– plants that grow in foreign land other than their native country
Indigenous
Naturalized
Evaluation of Crude Drugs1. Organoleptic evaluation
Aka macroscopic examinationUse of the senses
2. Microscopic evaluationUse of microscope to determine the purity and identity of the drug
Evaluation of Crude Drugs3. Pharmacologic evaluation
aka bioassay: using living thingsDRUG ANIMALDigoxin PigeonAtropine CatOxytocin Young adult
domesticated chicken (female)
Heparin Sheep’s bloodCod liver oil Rachitic ratParathyroid
hormoneDog
Tubocurarine (aka Head drop assay)
Rabbit, Rat
Evaluation of Crude Drugs4. Chemical evaluation
- best method to determine official potency- evaluate, identify the purity of substance
5. Physical evaluation- use of physical constants - ex. Boiling points, melting points
What are the FOUR General
Classification of Drugs?1. Morphology based on form2. Taxonomy based on
phylogeny3. Pharmacologic based on
drug action4. Chemical based on chemical
type of constituents
Important Scientific NamesANIS
Foeniculum vulgare
Important Scientific NamesAPPLE
Pyrus malus / Malus domestica
Important Scientific NamesATIS
Anona squamosa
Important Scientific Names
ATSUETE/ACHUETE
Bixa orellana
Important Scientific Names
AVOCADO
Persea americana
Important Scientific Names
BALANOY
Ocimum basilicum
Important Scientific Names
BALIMBING
Averrhoa carambola
Important Scientific Names
BANANA
Musa paradisiaca
Important Scientific Names
CHICHIRIKA
Catharanthus roseus
Important Scientific Names
CARROTS
Daucus carota
Important Scientific NamesCHICO
Achras zapota
Important Scientific Names
COTTON
Gossypium hirsutum
Important Scientific Names
DALANGHITA
Citrus nobilis
Important Scientific Names
DAMONG MARIA
Artemisia vulgaris
Important Scientific Names
DRAGON FRUIT
Hylocereus undatus
Important Scientific NamesDUHAT
Syzygium cumini
Important Scientific NamesGUGO
Entada phaseoloides
Important Scientific NamesIKMO
Piper betle
Important Scientific Names
IPIL-IPIL
Leucaena leucocephala
Important Scientific Names
KALAMANSI
Citrus microcarpa
Important Scientific NamesKASOY
Anacardium occidentale
Important Scientific Names
LABANOS
Raphanus sativus
Important Scientific Names
KAMIAS
Averrhoa bilimbi
Important Scientific Names
KANGKONG
Ipomea aquatica
Important Scientific Names
JACKFRUIT
Artocarpus heterophyllus
Important Scientific Names
LANSONES
Lansium domesticum
Important Scientific NamesLEMON
Citrus limon
Important Scientific NamesLINGA
Sesamum indicum
Important Scientific NamesLUYA
Zingiber officinale
Important Scientific NamesCORN
Zea mays
Important Scientific Names
MAKABUHAY
Tinospora rumphi / Tinospora crispa
Important Scientific Names
MAKAHIYA
Mimosa pudica
Important Scientific Names
MALUNGGAY
Moringa oleifera
Important Scientific Names
MANGOSTEEN
Garcinia mangostana
Important Scientific NamesMORAS
Vetiveria zizanioides / Andropogon zizanioides
Important Scientific NamesNIYOG
Cocos nucifera
Important Scientific Names
NONI/APATOT
Morinda citrifolia
Important Scientific Names
ORANGE
Citrus aurantium
Important Scientific Names
PAKWAN
Citrulus vulgaris
Important Scientific Names
POTATO
Solanum tuberosum
Important Scientific NamesPATOLA
Lufa acutangula
Important Scientific Names
PINEAPPLE
Ananas comosus
Important Scientific Names
SAMPALOK
Tamarindus indica
Important Scientific Names
SIBUYAS
Tamarindus indica
Important Scientific Names
SILI
Capsicum annuum
Important Scientific Names
SQUASH
Cucurbita maxima
Important Scientific NamesSUHA
Citrus grandis / Citrus maxima
Important Scientific Names
EGGPLANT
Solanum melongena
Important Scientific Names
TALUMPUNAY
Datura metel
Important Scientific Names
TANGLAD
Cymbopogon citratus
Important Scientific Names
TEA
Camellia sinensis
CARBOHYDRATES• These are polyhydroxy
aldehydes or polyhydroxyketonesCLASSIFICATION OF CHO:
• Monosaccharides – aka. Simple Sugars• Disaccharides – 2 sugars• Oligosaccharides – few sugars• Polysaccharides• Homoglycans• Heteroglycans
Monosaccharides# of C Name Example
2 Diose Hydroxyacetaldehyde
3 Triose Glyceraldehyde; dihydoxyacetone
4 Tetrose Erythrose
5 Pentose Ribose, 2 – deoxyribose; xylose
6 Hexose Glu, Fru, Gal, Man
7 Heptose Heptulose
8 Octose D – glycero D- mannoctulose
9 Nonose Neuraminic acid or also known as sialic acid
Monosaccharides(monos)
The Most Important Monosaccharide Is
• A Monosaccharide is made up of 1 sugar unit.
• Monos are reducing sugars.
HEXOSES
MonosaccharidesAldoses (e.g., glucose)
have an aldehyde group at one end.
Ketoses (e.g., fructose) have a keto group, usually
at C2.
C
C OHH
C HHO
C OHH
C OHH
CH2OH
D-glucose
OH
C HHO
C OHH
C OHH
CH2OH
CH2OH
C O
D-fructose
Monosaccharides(monos)
The Most Important Hexose Is
An aldohexoseAka physiologic sugar, blood sugar,
dextrose, grape sugarUses: nutrient and sweetening
agent
GLUCOSE
1 gram = 4 calories
FructoseA ketohexose
Identification test: Seliwanoff’s testAka. Fruit sugar or levuloseUses: food for diabetics, nutrient,
sweetening agent
GalactoseAn aldohexose
Identification test: mucic acid test
MannoseAn aldohexose
Identification test: osazone testMonosaccharide that readily forms
osazone crystals
Disaccharides• Formed by dehydration rxns
1. Sucrose (From Glu + Fru)Aka table sugar
- Non – reducing sugar Sources:
a. sugar cane (Saccharum officinarum)b. sugar beets (Beta vulgaris)c. sugar maple (Acer saccharum)
Disaccharides• Formed by dehydration rxns1. Sucrose (From Glu + Fru)
Uses:DemulcentSweetening agentManufacture of syrups Coating agentPreservative
Disaccharides• Formed by dehydration rxns2. Maltose (From Glu + Glu)
aka malt sugarproduced during the germination of barley (Hordeum vulgare)
3. Lactose (From Glu + Galactose)aka milk sugarisolated from Cow’s milk (Bos taurus)Lactose intolerance inability to secrete the enzyme lactase
Uses: stable diluent, in feeding formula
Disaccharides3. Lactose (From Glu + Galactose)
Lactulose produced by the alkaline rearrangement of lactose
Brand names: Lilac, Duphalac, Movelax
Uses: cathartic prevent portal systemic
encephalopathy
Oligosaccharides• Raffinose• Gentianose• Maltotriose• Sucralose
PolysaccharidesHomoglycan - one phase system
Heteroglycan- different
- Same type of sugar unit
- Different type of sugar
Examples:
StarchInulinDextranCellulose
Examples:
GumsMucilagesGlycosides
Polysaccharides• Starch - GLUCOSAN• Sources:
– Corn– Rice– Potato– Wheat– Cassava
• Starch - GLUCOSAN Propertie
sAmylose Amylopecti
nChemical composition
Composed of 250 – 300 glucose units linked by alpha 1, 4 glycosidic linkageAka LINEAR STARCH
Composed of 1000 or more glucose units linked by alpha 1,4 and alpha 1,6, glycosidic linkageAka BRANCHED STARCH
Water solubility
soluble insoluble
Iodine Test
Blue Violet
Percentage
25% 75%
General Uses of Starch1. Nutritive. 2. Demulcent. 3. Pharmaceutical uses as
tablets filler and binder. 4. Antipruritic: Baby paste®-
(Vitamed company) used in case of diaper rash, skin irritation (ZnO, Starch).
5. Industrial uses: papers, clothes.
6. Antidote in case of poisoning from Iodine.
Enzymes that break down Starch
1. Salivary amylase or ptyalin2. Pancreatic amylase
Starch Preparations:3. Pregelatinized starch4. Sodium starch glycollate5. Hetastarch
INULIN - FRUCTOSAN• Isolated from subterranean
organs of the plants belonging to plant family Compositae
• Abundant in Dandelion (Taraxacum officinale)
• Use: – in culture media as a fermentative
identifying agent for certain bacteria
– in special lab methods for the evaluation of renal function
• Filtered only by glomerular filtration
DEXTRAN – A GLUCOSAN• Produced by a microbe
Leuconostoc mesenteroides• Used as a plasma expander
Dextran Vs Dextrin?
A sweetening agentProduct of incomplete hydrolysis of starch
CELLULOSE – A GLUCOSAN• Preparations:
– Purified cotton/absorbent cotton from the hair of the seed of cultivated species of Gossypium hirsutum
– Pyroxylin or soluble guncotton obtained by the action of a mixture of nitric and sulfuric acids on cotton; it is a pharmaceutic acid in the preparation of collodion and flexible collodions, topical protectants
GUMS AND MUCILAGESPLANT EXUDATES
Acacia from Acacia senegal aka Gum arabic
Excellent emulsifier; a suspending agent; demulcent and emollient;An adhesive and binder in tablet granulations
Tragacanth from Astragalus gummifer
Suspending agent for insoluble powders in mixtures; emulsifier for oils and resins; MOST resistant to acid hydrolysis
Karaya from Sterculia urens aka sterculia gum
One of the least soluble of the plant gum exudates; a bulk laxative; agent for emulsions and suspensions; dental adhesive; ingredient in Movicol drug.
GUMS AND MUCILAGESSEED GUMS
Psyllium from Plantago psyllium aka plantago seed, plaintain seed
Used as cathartic; bulk laxative
Cydonium from Cydonia vulgaris aka quince seed
Ingredient in some wave setting lotions
Guar from Cyamopsis tetragonolobus aka guaran
Bulk laxative, thickening agent, tablet binder; disintegrator
Locust bean gum from Ceratonia siliqua aka carob pulp, St. John’s bread
Thickening agent, stabilizer
GUMS AND MUCILAGESMARINE GUMS
Agar from Gelidium cartilagineum and Gracilaria confervoides aka Japanese isinglas
Laxative, suspending agent, emulsifier, gelating agent for suppositories; tablet disintegrant; extensively used as a gel in culture media and aid in food processing
Sodium alginate from Macrocystis pyrifera aka algin
Brown seaweed; suspending agent; food industry (ice creamm chocolate milk, salad dressings, icings, confectionery)
Carrageenan from Chondus crispus and Gigartina mamillosa
Red algae, red seaweeds; used to form gels, stabilizer for emulsions and suspensions; demulcent; laxative
GUMS AND MUCILAGESMICROBIAL GUM
Xanthan gum from Xanthomonas campestris
Excellent emulsifier and suspending agent; pseudoplastic property of this gum enable toothpastes and ointments both to hold their shape and to spread readily.
• Pectin– Isolated from the inner rind of citrus
fruits and apple pomace.– Used as a protectant, suspending agent
and ingredient in many antidiarrheal formulations
GUMS AND MUCILAGES
Glycosides• Known as • Have two portions
–Glycone –Aglycone
Sugar portion
Non - Sugar portion ; GENIN
SUGAR ETHERS
• Solubility: glycosides are water soluble
compounds and insoluble in the organic solvents.
Glycone part: water soluble, insoluble in the organic solvents.
Aglycone part: water insoluble, soluble in the organic solvents.
Some glycosides are soluble in alcohol.
Stability of Glycosides:1- Effect of acid hydrolysis:• Acids split sugars from the
aglycones.• The acetal linkage is more readily
cleaved than the linkage between the individual sugars of the sugar chain.
• C-glycosides are resistant to acid hydrolysis.
2- Effect of alkaline hydrolysis:A- Strong alkalis:
• Hydrolysis of ester groups.• Opening of lactone rings e.g.
Cardiac glycosides.
B- Mild alkalis:• Hydrolysis of ester groups e.g.
Lanatoside A to Purpurea A• Opening of lactone rings e.g.
Cardiac glycosides.
3- Enzymatic hydrolysis:
– Split the sugars stepwise starting from the terminal sugars.
– All plants producing glycosides have enzyme that can hydrolyze these glycosides.
– Enzymes are specific for the type of glycosidic linkages:• Emulsin can hydrolyze b- glycosides• Invertase can hydrolyze a- glycosides• Myrosin can hydrolyze s-glycosides.
Classification of the glycoside based on the chemical nature of the
aglycone part.1. Cardioactive group2. Anthraquinone group3. Saponin group4. Cyanophore group5. Isothiocyanate group6. Flavonol group7. Alcohol group
Classification of the glycoside based on the chemical nature of the
aglycone part.8. Aldehyde group9. Lactone group10. Phenol group
CARDIOACTIVE GLYCOSIDES Identification Test:
Aglycone part has steroidal nucleus
cyclopentanoperhydrophenanthrene
Classification of the aglycone: 1. Cardenolide (one double bond, lactone ring) : Has five member lactone ring (unsaturated) attached at C17 B
position of steroidal nucleus; MORE ABUNDANT IN NATURE2. Bufadienolide: (contain two double bonds, lactone ring) Has six member ( unsaturated ) lactone ring attached at C-17
alpha – position; FIRST OBTAINED FROM BULL FROG
Keller – Killiani Test
Use: Inotropic agents
PLANTS CONTAINING CARDIOACTIVE
GLYCOSIDES
SCIENTIFIC NAMES
Grecian Foxglove Digitalis lanataFoxglove Digitalis purpureaLily of the Valley or Convallaria
Convallaria majalis
Adonis or Peasant’s eye Adonis vernalisStrophantus Strophantus kombeBlack Hellebore / Christmas rose
Helleborus niger
Apocynum or Black Indian Hemp
Apocynum canabinum
Adelfa Nerium oleanderSquill Urgenia maritima
Chemical tests :
1) Keller Kiliani test : C.G + CH3COOH + H2SO4 + FeCl3 brown
2) Legal test : C.G + pyridine sodium nitroprusside Red to pink
General properties : 1- Amorphous powder 2-bitter taste 3- sol. In H2O 4-Insol. In Org. solvents5- Very toxic compounds 6- Odorless
Anthraquinone group of glycosides
Aglycone portion: Anthracene
Identification test: Borntrager’s test
Use: Drastic cathartics
except: Chrysarobin very irritating
used as a keratolytic agent
Anthraquinone glycosidesCascara sagrada
LN: rhamnus purshianaEN: Sacred barkSyn: Chitten wood barkSN: Rhamnus purshianusFN: RhamnaceaePU: dried barkConst: Emodin; frangulinUses: cathartic; restores the natural tone to
the colon (1 mL = bitter cascara; 5mL = sweet cascara) PP: Cas – Evac
Anthraquinone glycosidesFrangula
Syn: buckthorn buck
- The dried bark of Rhamnus frangula Linne.
Use: cathartic
PP: Movicol
Anthraquinone glycosidesAloe
From Aloe barbadensis, Aloe vera Linne, Aloe ferox, Aloe africana and Aloe spicata.
Syn: Cape aloe, Curacao aloe FN: LiliaceaeAloe shining, bitter substanceVera trueBarbadensis from Barbados islandFerox wild or ferociousAfricana habitat of plant from Southern
AfricaSpicata flowers in spikes
Anthraquinone glycosidesAloe
Principal constituent: barbaloin (aloe – emodin anthrone C-10 glucoside), aloin
Uses: cathartics, treatment of burns, emollient, moisturizer
RhubarbSyn: Rheum, chinese rhubarbFrom Rheum officinale, Rheum palmatumFN: PolygonaceaeRheum from the latin name Rha of the
Volga river where the species grow
Anthraquinone glycosidesRhubarb
Palmatum large spreading leaves
Principal constituents: rhein anthronesUse: Cathartic
SennaFrom Cassia acutifolia (Syn: Alexandria
senna), from Cassia angustifolia (Syn: Tinnevelly senna)
FN: Leguminosae
Anthraquinone glycosidesSenna
Senna arabic sena, native name of the drug
Cassia hebrew qetsiah, to cut offAcutifolia latin, sharply pointed leavesAngustifolia latin, narrow – leavedBlue green leaves are the best; yellowish
leaves are the poorestConst: sennosideUses: cathartic, dose = 2gPP: Senokot, Gentlax, Senexon, Senokap,
Senolax
Anthraquinone glycosidesChrysarobin
From Goa powder SN: Andira ararobaFN: LeguminosaeConst: chrysophenolanthrone or
chrysophenolanthranol; emodinanthrone; dihydroemodinanthrone
Uses: keratolytic agent; treatment of psoriasis, trichophytosis, and chronic eczema.
PP: Anthra Derm, Drithocreme, Lasan
Anthraquinone glycosidesDanthron
Syn: chrysazin, 1-8 dihydroxyanthraquinoneUse: cathartic, dose = 75 to 150mgPP: Akshun, Dorbane, Modane, Tonelax
Danthron + surfactantPP: Doctate P, Dorbantyl, Doxan, Doxidan,
Guarsol, Pro-Cal-Thron, Valax
Saponin group of glycoside
SSSS
oaplike properties
teroidal
apogenin aglycone
apotoxin toxic aglycone
Saponin group of glycoside
Chemical Tests:
a. Froth Test formation of honeycomb froth (after 10 mins)
b. Hemolysis test in blood agar medium
c. Keller – Killiani test to decide 2 deoxysugar usually found in steroids
Saponin group of glycoside
1. Glycyrrhiza or Licorice (Glycyrrhiza glabra)1. 50x sweeter than sugar2. Easily oxidized to glycerrhetic acid3. Uses: foaminess of root beer
treatment of Addison’s diseaseantiinflammatory
2. Dioscorea (Dioscorea floribunda, Dioscorea spiculiflora, Yam)1. Dioscorea floribunda Best source of steroid2. Dioscorea spiculiflora contains diosgenin w/c
is a glucocorticoid precursor.
Saponin group of glycoside
3. Ginseng (Panax ginseng, Panax quinquefolius)1. Panax ginseng Asian / Korean ginseng2. Panax quinquefolius American ginseng
Constituents:panaxosides, ginsenosides and chikusetsusaponins
Uses:aphrodisiac, tonic
Cyanogenic GlycosidesCyanogenic glycosides (Cyanogentic or
Cyanophore Glycosides) are O-glycosides yielding HCN gas on hydrolysis .
They are condensation products of HCN to a carbonyl compounds (Cyanohydrin).
C
R
R
O C
R
R OH
CNHCN
C
R
R O-Sug
CNGlycosylation
Unstable Stable
1- AmygdalinSource: Bitter Almond.Structures: It is a Bioside of
mandelonitrile.
CH
CN
O glc glc
CH
CN
O glc
Amygdalin Prunasin
1-6 blinkage
CH
CN
O H
Mandilonitril
CHOHCN +
Amygdalase Prunase
2- LinamarinSource: Linseed.Structures: It is the glycosidic derivative of
the cyanohydrin of acetone.
Uses:Linamarin has a molluscecidal activity.Amygdalin is used for the preparation of
Benzaldehyde.Cyanogenic glycosides have role in cancer
treatment.
CH3C
CNH3C
O glc
3- Laetrile or Vitamin B17
Source: obtained from seed of Rosaceae Use: Has anticancer claims
ThioglycosideGlucosinolates- Sulfur Glycosides
• They are S-glycosides widely distributed in family Cruciferae.
• Sinigrin: In seeds of Brassica nigra (black mustard).
• Sinalbin: In Seeds of Brassica alba (white mustard).
• Uses: Rubefacients, Counter irritants and condiment.
H2CHC C
H2
CN-O-SO3K
S-Glc
Sinigrin
These plants contain also enzyme myrosin (myrosinase) which hydrolyze these glycosides yields mustard oilsProperties of Mustard oil Sinigrin (allyl isothiocyanate) :1.Irritant for mucous membrane2.Volatile3.Pungent4.Characteristic odor
Also called volatile mustard oil.The uses of Mustard seeds : counter irritant rubefacient, condiment, emetic in large doses.Drug :Acne aid soap®- AgisTreatment of Acne .
Sinalbin (from white mustard) : upon hydrolysis yield acrinyl isothiocyanate.
Properties of acrinyl isothiocyanate.1.Less irritant than allyl isothiocynate.2.Less volatile.3.Odorless.4.Pungent.
Uses of white mustard seedsCondiment, carminative, counter irritant, emetic
Garlic• It consists of the bulb of Allium sativum Fam.
Liliaceae.• The intact cells of garlic contain an odorless,
sulfur-containing amino acid derivative (+)-S-allyl-L-cysteine sulfoxide, commonly known as alliin.
• Alliin is hydrolyzed by the effect of alliinase enzyme present in different cells after crushing into allicin (diallyl thiosulfinate).
• Allicin is responsible for the characteristic odor and flavor of garlic.
• Allicin is a potent antibacterial, antihyperlipidemic, and it inhibits platelet aggregation and enhances the blood fibrinolytic activity.
SH
O
NH2
COOH SS
O
Alliinase + H2O
Alliin Allicin
Alcoholic group of glycosides
Such as: Salicin which obtained from Salix bark, Willow bark, Poplar barks.
Salicin is obtained from several species of Salix and Populus. (Salix purpurea and S. fragilis)
Salicin hydrolyzed by: 1.Enzyme emulsin2.Acid like HCl,HNO3
3.Alkaline solutions like NaOH
Populin (benzoyl-salicin), associated with salicin in the barks of Salicaceae.
Alcoholic Glycosides1- Salicin
Source: Salix species (Willow bark).Nature: Primary achholic and Phenolic
glycoside (monoside).Uses: Analgesic- Antipyretic- Anti-
inflammatory.
CH2OH
O-glc
Enzyme
CH2OH
OHSaligenin
(Salicyl alch.)
+Glucose
AcidO
CH2OH
HOH2C
+Glucose
Saliretin
The effect of salicylic acid :
1. Analgesic.2. Anti-pyretic.3. Anti-coagulant (anticlotting agent).4. Anti- inflammatory activity (Rheumatism)5. Wart and corn remover6. Prevents colon cancer
Phenolic group of glycosides
ABU
Arbutin ; Astringent
Bearberry (isolated from)
Uva Ursi
OH
O-glc
OCH3
O-glc
OH
OH
+ GlucoseHydrolysis
Hydroquinone
ArbutinMethylarbutin
Arbutin & Methyl Arbutin
Source: Uva Ursi (Bearberry leaves).Nature: Primary Phenolic glycoside
(monoside).Uses: Diuretic- Bactericidal.
Aldehydic group of glycoside Vanilla a drug that has an aldehydic
aglycone known as vanillin (methylprotocatechuic aldehyde).
Green vanilla has two glycosides, known as1. Glucovanillin which obtained from :
Vanilla beans (fruits) – curing process** Vanillin : volatile oil which used as flavoring
agent** vanillin : 1.phenolic group volatile oils 2.aldehyde group of volatile oils
- yields glucose and vanillin2. Glucovanillic alcohol- yields glucose and vanillic alcohol oxidized to vannillic aldehyde (vanillin)
Aldehydic Glycosides1- Glucovanillin
Source: Vanilla pods.Uses: Flavouring agent- Spray reagent.
CHO
O-glc
OCH3
CHO
OH
OCH3
Enzymatic Hydrolysis
Vanillin
Green vanilla podsBitter in taste
Odourless
Brown vanilla podsSweet in tasteVanilla odour
+ Glucose
Glucovanillin
Flavonoids Large group of glycosides which widely
distributed in the plants kingdom and in all plants parts (leaves, roots, rhizomes, fruits peels)
Various colors in flowers( yellow, orange, red, purple.)
benzo-gama-pyrone derivatives, chemical structure based on (C6 C3 C6 ).
USES:1. Increase elasticity of blood vessels specially
Rutin and hesperidin which known as vitamin (p)
2. Anti inflammatory activity like Taxifolin
3. Anti spasmodic activity like Thyme and sage flavonoids.
4. Cytostatic activity.
Classification of Flavonoids according to the main nucleus
Flavonoids glycosides
flavonoids Main nucleus
Quercitrin Rhamnoglucosid
e
quercetin Flavonol unsaturated
yellowVitexin Diosmetin Flavone (unsat)
YellowNaringen Hesperitin Flavanone
(satur)colorless
Lactone GlycosidesGlycosides containing coumarin are
rare.
CPC
oumarin from Tonka beans (Dipteryx odorata)
antharides; aka blistering fly, russian fly or spanish fly
hotosensitizing furocoumarins; treatment of vitiligo
Tannins are polyphenols that are obtained from various parts of different plants belonging to multiple species.
Derived from the word “tanning” (meant converting animal hides to leather through chemical processes
Tannins are classified into:
1.True tannins (hydrolysable)+ (non-hydrolysable).
2. Pseudo tannins.
Differences
Hydrolyzable
Non-Hydrolyzable
Chemically related to
Pyrogallol Catechol
+ HCl Phenolic acids & sugars
Polymerize forming Phlobaphenes (red compounds)
+ ferric oxide
Bluish black ppt Greenish black ppt
Resultant leather produces
Pale – colored sediment called “Bloom” (pale color from creamy or yellowish to light brown
Tanner’s red; solid color leathers of pink, red or dark brown
+ bromine water test
( - ) ppt ( + ) ppt
USESINDUSTRIAL MEDICINAL Dyes Leather
Astringent Precipitants
Tannin – containing Plants1. Hamamelis or Witch Hazel leaves
(Hamamelis virginiana) Const: hamamelitannin
2. Nutgall (from plant Quercus infectoria and from insect producing nutgall Cynips tinctoriae)
3. Betel nut (Areca catechu)4. Tea (Camellia sinensis)
Alkaloids
Definition Alkaloids are basic nitrogen containing
compounds. They are generally obtained from plants, animals and microorganisms and often demonstrate a marked physiological action
ALKALOID DESCRIPTION
Alkaloids are basic -they form water soluble salts. Most alkaloids are well-defined crystalline substances which unite with acids to form salts. In plants, they may exist
in the free state, as salts or as N-oxides. Occur in a limited number of plants.
Nucleic acid exists in all plants, whereas, morphine exists in only one plant species .
ALKALOID DESCRIPTION
Alkaloids are basic -they form water soluble salts. Most alkaloids are well-defined crystalline substances which unite with acids to form salts. In plants, they may exist
in the free state, as salts or as N-oxides. Occur in a limited number of plants.
Nucleic acid exists in all plants, whereas, morphine exists in only one plant species .
TESTS FOR ALKALOIDSMost alkaloids are precipitated from neutral
or slightly acidic solution by Dragendorff's reagent (solution of
potassium bismuth iodide)orange coloured precipitate.
Mayer's reagent (potassio mercuric iodide solution) Cream coloured precipitate.
Wagner’s reagent (iodine in potassium iodide) red-brown precipitate
Hagers reagent (picric acid) yellow precipitate
Caffeine does precipitate
OCCURRENCE, DISTRIBUTION& LOCATION OF ALKALOIDSOccur in bacteria(Pseudomonas aeruginosa) and
rarely in fungi (pscilocin from hallucinogenic mushrooms).
Some alkaloids occur in several genera from different species (caffeine), but most occur in closely related species.
Some occur in certain families (hyoscyamine), while others occur only in a specific species (morphine).
Rarely do plants contain more than 1 type of alkaloid.
All alkaloids of one plant will have a common biogenenetic origin
• Alkaloids occur in all plant parts, but are usually localized in one organ (e.g. the bark or seeds).
• Within the plant, [alkaloid] can vary widely from part to part –some parts may contain no alkaloids.
• Occasionally, different alkaloids also form in different parts of the plant.
• Alkaloid concentrations occur in wide ranges –e.g. Madagascar periwinkle contains 3g per (anti-cancer) alkaloids per tonne of leaves.
PHYSICAL-CHEMICAL PROPERTIES OF ALKALOIDSMW: 100 –900Most bases which do not contain O2 are
liquid at room temperature (nicotine), while those that do are solids. In rare cases they are colored.
Most solid bases rotate the plane of polarized light, have high melting points.
Normally are not soluble in water (occasionally slightly soluble).
Soluble in a polar or slightly polar organic solvents. Soluble in concentrated hydroalcoholic solutions
The basicity of alkaloids depends on the availability of the lone pair of e-on the N2 atoms: e-donating groups enhance basicity, while e-withdrawing groups decrease it.
Because some alkaloids have a carbonyl group on the amide, they can also be neutral (colchicine & piperine).
Basic characteristic renders complex alkaloids unstable, so that in solution they are sensitive to heat, light & oxygen.
Basic character of alkaloids also allows them to form salts with mineral acids (such as hydrochlorides, nitrates and sulphates) or inorganic acids (tartrates, sulfamates).
Alkaloid salts are soluble in water and dilute alcohols.Solid salts can be conserved well and are a common
commercial form of alkaloids.
NAMING OF ALKALOIDSNumerous methods can be used to name alkaloids1-Generic plant name –atropine from Atropa belladonna2-Specific name of the plant –cocaine from Erythroxylum coca.3-Common name of the herb –ergotamine from ergot (rye)4-Physiological action of the plant –emetine producing emesis5-Other –e.g. morphine derived from ancient Greek mythology –Morpheus –god of dreams
EXTRACTION OF ALKALOIDS
Extraction is based on the basicity of alkaloids and on the fact that they normally occur in plants as salts (i.e.: on the solubility of bases and salts in water and organic solvents).
Herbs often contain other materials which can interfere with extraction such as large amounts of fat, waxes, terpenes, pigments and other lipophilic substances (e.g by forming emulsions) –avoided by defatting the crushed herb (using petroleum ether and hexane.
EXTRACTION OF ALKALOIDS
Extraction method normally depends on the raw material, the purpose of extraction & the scale on which is to be performed.
For research purposes: chromatography allows for quick and reliable results.
If larger amounts of alkaloids need to be extracted, one of the following methods can be used.
GENERAL METHOD
Step 1• Powdered, defatted herb is
mixed with an alkaline aqueous solution.
• Free bases are then extracted with organic solvents.
• Normally aqueous ammonia is used, but a carbonate solution is used when alkaloids contain fragile elements such as a ester or lactone.
GENERAL METHOD• In some cases, e.g.
Cinchona bark, a mixture of calcium hydroxide & sodium hydroxide should be used as the alkaloids are bound to tannins.
• Organic solvent: chloroform, dichloromethane or ethyl acetate –depends on the toxicity, safety, cost & ease of recovery and recycling of the solvent).
Step II
Organic solvent containing alkaloids (bases) is separated from residue & concentrated by distillation under pressure if needed.
Solvent is stirred with an acidic aqueous solution: alkaloids go into the solution as salts. Impurities remain in the organic phase.
• Aqueous solution of alkaloid salts is washed with an apolar solvent (hexane)
• Alkalinized with a base using an organic solvent not miscible with water.
• Alkaloids precipitate and dissolve in the organic phase.
• Extraction of aqueous phase continues till all alkaloids have moved into the organic phase (tested when Mayer’s reaction on the aqueous phase becomes negative).
• This purification step may be carried out in a separation funnel or in centrifugal extractors
Step IIIOrganic solvent containing alkaloid bases is
decanted, freed from water traces (drying over anhydrous salt e.g. sodium sulphate) and evaporated under reduced pressure.
A dry residue remains: total basic alkaloids.
Extraction of liquid alkaloids
2 Methods possible
1-Plant powder is extracted directly
with acidified water
2-Plant powder is extracted with
acidified alcoholic or a hydroalcoholic
solution. This is then followed by
distillation under vacuum (eliminates
that alcohol, leaving behind and acidic
aqueous solution of alkaloid salts)
Classification of Alkaloids1. Biological origin
Sedatives : MorphineVasodilatation : Ephedrine, Ergonovine . Local anesthetic : CocaineHallucinating : Mescaline, Psilocybin.
2-Biosynthetic pathway Ornithine- Tropane, Pyrrolidine, PyrrolizidineTyrosine-Benzyl isoquinolineTryptophane- Indole alkaloids, QuinolinePyridine- PyridineLysine- Quinolizidine, Piperidine
3- Chemical classification
True (Typical) alkaloids that are derived from amino acids and have nitrogen in a heterocyclic ring. e.g Atropine
Proto alkaloids that are derived from amino acids and do not have nitrogen in a heterocyclic ring. e.g Ephedrine
Pseudo alkaloids that are not derived from amino acids but have nitrogen in a heterocyclic ring. e.g Caffeine
False alkaloids are non alkaloids give false positive reaction with alkaloidal reagents.
A. Proto alkaloids
These are also called Non heterocyclic or Atypical alkaloids or Biological amines.
These are less commonly found in nature. These molecules have a nitrogen atom
which is not a part of any ring system. Examples of these include ephedrine,
colchicine, erythromycin and taxol etc. Table below shows the chemical structure
and biological significance of these compounds:
Name Structure Biological Significance
Ephedrine
Adrenergic agent-used for asthma and hay fever
Colchicine
Relieves gout
Erythromycin
Antibiotic
Taxol (Paclitaxel)
Used in the treatment of ovarian cancer, breast cancer and non-small cell lung cancer
B. Heterocyclic Alkaloids or Typical Alkaloids:Structurally these have the nitrogen as a
part of a cyclic ring system. These are more commonly found in nature. Heterocyclic alkaloids are further
subdivided into 14 groups based on the ring structure containing the nitrogen
No. Heterocycle Example
1.
Pyrrole and Pyrrolidine
Hygrine, Stachydrine
2.
Pyrrolizidine
Senecionine, Symphitine, Echimidine, Seneciphylline
3.
Pyridine and Piperidine
Lobeline, Nicotine, Piperine, Conine, Trigonelline
4.
Tropane (piperidine/N-methyl-pyrrolidine)
Cocaine, Atropine, Hyoscyamine, Hyoscine
5.
Quinoline
Quinine, Quinidine, Cinchonine, Cinchonidine
6.
Isoquinoline
Morphine, Emetine, Papaverine, Narcotine, Tubocurarine, Codeine
7.
Aporphine (reduced isoquinoline/naphthalene)
Boldine
8.
Quinolizidine
Lupanine, Cytisine, Laburnine, Sparteine
9.
Indole or Benzopyrole
Ergometrine, Vinblastine, Vincristine, Strychnine, Brucine, Ergotamine, Yohimbine, Reserpine, Serpentine, Physostigmine
10.
Indolizidine
Castanospermine, Swainsonine
11.
Imidazole or glyoxaline
Pilocarpine, Pilosine
12.
Purine (pyrimidine/imidazole)
Caffeine, Theobromine
13. Steroidal (some combined as glycosides)*
Conessine, Solanidine
14. Terpenoid*
Aconitine, lycaconitine, Aconine
*Note- Steroidal and terpenoid classes are also treated as separate classes or along with glycosides.
Lipids
LIPIDS• Such as fixed oils, fats and
waxes are esters of long – chain fatty acids and alcohols, or of closely related derivatives.
• SIMPLE: fixed oils, fats and waxes
• COMPLEX: phosphatides, lecithins
LIPIDS• CHIEF difference between
these substances is the type of alcohol
1) In fixed oils and fats, the alcohol is glycerol, combines with the fatty acids
2) In waxes, the alcohol has a higher molecular weight, e.g., cetyl alcohol [CH3(CH2)15OH]
Characteristics Volatile Oils Fixed Oils
Chemical consitituents
Mostly consist of terpenoids; mixtures of eleoptenes and stearoptenes
Mostly consist of glyceryl esters of fatty acids
Spot Test Does not leave any spot on filter paper
Leaves a permanent spot on paper
Saponification Test
Not applicable Saponifies with alkalies
Obtained by distillation evaporationRancidity Not applicable Becomes rancid on
storageExposure to air and light
Easily oxidized and undergo resinification
Not applicable
Refractive index High LowFragrance Distinctly marked and
specificNot applicable
FATS VERSUS FIXED OILS
Animal fats Plant fats or vegetable fatsSolid at room temperature Liquid at room temperature
More stable Less stableContain saturated glycerides e.g. glyceryl stearate
Contain unsaturated glycerides e.g. glyceryl oleate
Iodine number will be relatively less
Iodine number will be more than compared to animal fats
Relatively higher value of Reichert-Meissl number
Relatively lower value of Reichert-Meissl number
Oxidative rancidity is observed more frequently
Oxidative rancidity is relatively less
Relatively higher melting point Low melting pointStored in liver, beneath the skin etc.
Stored in fruits and seeds
Example: butter fat, beef fat Example: coconut oil, olive oil, sunflower oil
Iodine number denote the degree of un-saturation in fatty acids
Reichert-Meissl number indicate how much volatile fatty acid can be extracted from a fat through saponification
DEFINITION OF SOME TERMS
Applications of fixed oils and fats1. Soap manufacture
2. Suppositories, tablet coating
3. Dietary supplements
4. Emulsifying agents
5. Manufacture of paints, varnishes and lubricants
6. Therapeutic uses (castor oil).
Examples • Castor oil• Olive oil• Peanut oil• Soybean oil• Sesame oil• Almond oil• Cottonseed oil• Corn oil• Safflower oil• Cocoa butter
• Wax is also produced by insects, e.g. the honeycombs of bees and wasps.
USES OF WAX1.Wax is used in pharmacy
to make soft ointments harder and to prepare lip salves.
2.The technical uses of waxes are substantial, e.g. in shoe polishes and car waxes.
Examples
• Jojoba wax (Simmondsia chinensis)
• Carnauba wax (Copernicia cerifera)
• Beeswax (Apis mellifera)
VOLATILE OILS• Aka essences, essential oils or
ethereal oils
VOLATILE OILSAll official volatile oils
are of vegetable origin.
Normally pre-exist in the plant – stored in a special secretory tissue (e.g. Citrus peel oil cells or oil ducts in umbelliferous fruits).
EXCEPTION: Oil of bitter almond – formed by hydrolysis of the glycosides.
USES OF VOLATILE OILS• Therapeutically (Oil of
Eucalyptus)• Flavouring (Oil of Lemon)• Perfumery (Oil of Rose)• Starting materials to
synthesize other compounds (Oil of Turpentine)
• Anti-septic – due to high phenols (Oil of Thyme). Also as a preservative (oils interfere with bacterial respiration)
• Anti-spasmodic (Ginger, Lemon balm, Rosemary, Peppermint, Chamomile, Fennel, Caraway)
• Aromatherapy
DEFINITION OF VOLATILE OILS
Volatile oils are products which are generally complex in composition, consisting of the volatile principles contained in plants, and are more or less modified during the preparation process.
Only 2 procedures may be used to prepare official oils
i. Steam distillationii. Expression
4 Main types of volatile oilsiii. Concretesiv. Pomadesv. Resinoidsvi. Absolutes
CONCRETESPrepared from raw
materials of vegetable origin (bark, flowers, leafs, roots etc.)
Extracted by HC type solvents, rather than distillation or expression – Becomes necessary when the essential oil is adversely affected by hot water or steam (e.g. jasmine).
Produces a more true-to-nature fragrance.
CONCRETESConcretes contain
about 50 % wax and 50 % essential oil (jasmine).
Ylang ylang (concrete volatile) contains 80 % essential oil and 20 % wax.
Advantages of concretes: they are more stable and concentrated than pure essential oils.
POMADESTrue pomades are
(volatile oil) products of a process known as enfleurage (hot or cold).
Enfleurage is used for obtaining aromatic materials from flowers containing volatile oils to produce perfume long after they were cut.
ENFLEURAGE: METHODA glass plate is covered with
a thin coating of especially prepared and odourless fat (called a chassis).
The freshly cut flowers are individually laid on to the fat which in time becomes saturated with their essential oils. The flowers are renewed with fresh material.
Eventually the fragrance-saturated fat, known as pomade, may be treated with alcohol to extract the oil from the fat.
RESINOIDSPrepared from natural
resinous material (dried material) by extraction with a non-aqueous solvent, e.g. Petroleum ether or hexane.
E.g. Balsams – Peru balsam or benzoin; resins (amber or mastic); Oleoresin (copaiba balsam and turpentine); Oleogum resins (frankincense and myrrh)
RESINOIDSCan be viscous
liquids, semi-solid or solid.
Usually homogeneous mass of non-crystalline character.
Uses: in perfumery as fixatives to prolong the effect of a fragrance.
ABSOLUTESObtained from a
concrete, pomade, or a resinoid by alcoholic extraction.
The extraction process may be repeated.
The ethanol solution is cooled & filtered to eliminate waxes.
The ethanol is then removed by distillation.
They are usually highly concentrated viscous liquids.
Fx OF VOLATILE OILSIn most cases, the
biological function of the terpenoids of essential oils remains obscure – it is thought that they play an ecological role – protection from predators & attraction of pollinators.
LOCALIZATIONSynthesis & accumulation of essential oils
are generally associated with the presence of specialized histological structures, often located on or near the surface of the plant:
- Oil cells of Zingiberaceae- Glandular trichomes of Lamiaceae- Secretory cavities of Myrtaceae or Rutaceae
- Secretory canals of Apiaceae or Astereraceae (Compositeae)
VOLATILE OIL COMPOSITION• Mixtures of HC’s and oxygenated
compounds derived from these HC’s.– Oil of turpentine – mainly HC’s– Oil of Clove – mainly oxygenated
compounds• EXCEPTION: Oils derived from
glycosides (e.g. bitter almond oil & mustard oil).
• Oxygenated compounds – responsible for the odour/smell of the oil. They are slightly water soluble – Rose water & Orange Water; more alcohol soluble.
• Most volatile oils are terpenoid. Some are aromatic (benzene) derivatives mixed with terpenes.
• Some compounds are aromatic, but terpenoid in origin (e.g. Thymol – Thyme)
CHEMICAL COMPOSITIONVolatile oils are divided into 2 main classes
based on their biosynthetic origin
i. Terpene derivatives (formed via the acetate mevalonic acid pathway)
ii. Aromatic compounds (formed via the shikimic acid-phenylpropanoid route)
iii. Miscellaneous Origin
Terpene derivatives
CH3
OH
H3C CH3
Menthol
(peppermint oil)
CH3
O
H3C CH2
Carvone
(caraway oil)
CH3
H3C CH3
OH
Thymol
(thyme oil)
Aromatic compounds
OH
OCH3
Eugenol(clove oil)
OCH3
CH3
Anethole(anise oils)
CHO
Cinnamaldehyde(cinnamon oil)
CH2
A. TERPENESTerpenes, or
terpenoids, are the largest group of secondary products (metabolites).
They are all formed from acetyl CoA or glycolytic intermediates.
CLASSIFICATION OF TERPENES
All terpenes are formed from 5-C elements
Isoprene is the basic structural element.
CLASSIFICATION OF TERPENES
Terpenes are classified by the number of 5-C atoms they contain
10-Carbon terpenes (contain 2 C-5 units) – monoterpenes
15- Carbon terpenes (3 C-5 units) are called sesquiterpenes.
20-carbon terpenes (4 C-5 units) are diterpenes.Larger terpenes (30 Carbons) are called
triterpenes (triterpenoids), 40 Carbons – called tetraterpenes and polyterpenoids.
TERPENOIDSTerpenoids contain only
the most volatile terpenes (i.e. molecular weight is not too high) mono and sesquiterpenes
May occur as oxygenated derivatives, e.g. alcohols, aldehydes, ketones, phenols, oxides & esters.
EXAMPLES OF TERPENESi. LIMONENEii. MENTHOLiii.BORNEOLiv. SESQUITERPENES
i. LIMONENEStructural
classification: Monocyclic terpene
Functional Classification: Unsaturated HC
Occurrence: Citrus fruit
ii. MENTHOLStructural
classification:Monocyclic with
hydroxyl group
Functional classification: Alcohol
Occurrence: Peppermint
iii. BORNEOL
Functional Classification: ////
Occurrence: Cinnamon
iv. SESQUITERPENES(Contain 3 isoprene
units)
Acyclic – E.g. Farnesol
Monocyclic – E.g. Bisobolol
Bicyclic e.g. Chamezulene (Chamomile)
B. AROMATIC COMPOUNDS
Many are phenols are phenol esters
E.g. Vanillin
PROPERTIES OF VOLATILE OILS• Almost entirely volatile
without decomposition.• Density: Most are less than
1g/ml.– 2 are heavier – Oil of Cinnamon
and Clove oil.• Soluble in ether, chloroform
& alcohol.• Slightly soluble in water:
give it a characteristic odour & taste.
• Leaves a temporary translucent stain on paper which disappears as the oil volatilizes.
• Most are colorless. Oxidize on exposure to air and resinify colour becomes darker (odour changes slightly).
• All are characteristic odors.• Most are optically active.
PRODUCTION OF ESSENTIAL OILS
Essential oils may be produced i. By steam
- Simple steam distillation- Saturated steam distillation- Hydrodiffusion
ii. By expressioniii. Other Methods
Concretes & Resinoids may be producediv. By solvent extractionv. By methods using oils & fatsvi. By extraction by supercritical gasses
ESSENTIAL OILS: i.STEAM DISTILLATION
a. SIMPLE STEAM DISTILLATIONPlant material is immersed directly in
a still filled with water. This is then brought to a boil.
Heterogeneous vapours are condensed on a cold surface.
Essential oil separates based on difference in density and immiscibility.
b. SATURATED STEAMPlant does not come into contact with the
water steam is injected through the plant material placed on perforated trays.
It is possible to operate under moderate pressure.
Advantages: Limits the alteration of the constituents of the oil
It shortens the duration of the treatmentIt conserves energyIt can also be conducted on on-line in
automated set ups.
c. HYDRODIFFUSIONPulses of steam is sent through the
plant material at very low pressure from (top to bottom).
ADVANTAGE: Normally produces a product of high quality.
Saves time and energy.
ii. EXPRESSION (E.G.OF CITRUS
EPICARPS)The rind is lacerated, and the contents of
the ruptured secretory cavities are recovered.
CLASSIC PROCESS: an abrasive action is applied on the surface of the fruit in a flow of water. The solid waste is eliminated, and the essential oil separated from the aqueous phase by centrifugation.
OTHER machines break the cavities by depression, and collect the essential oil directly prevents the degradation linked to the action of water.
EXPRESSION OF CITRUS EPICARPS
Most facilities allow for the simultaneous or sequential recovery of the fruit juice and of the essential oil, by collecting the oil with a spray of water after the abrasion (scarification – puncture by pins) before or during the expression of the fruit juice.
Enzymatic treatment of the residual water allows recycling, and markedly increases the final yield of essential oil.
Citrus oils are also obtained directly from the fruit juices (by vacuum de-oiling)
iii. OTHER METHODS- Steam distillation by microwaves under
vacuum. In this procedure, the plant is heated selectively by microwave radiation in a chamber inside which the pressure is reduced sequentially.
- fresh plants require no added water.
- ADVANTAGE: This method is fast, consumes little energy and yields a product which is most often of a higher quality than the traditional steam distillation product.
PRODUCTION OF CONCRETES & RESINOIDS
i. SOLVENT EXTRACTIONExtraction is generally preceded by a
process of: bruising the fresh, wilted or semi-desiccated organs, chopping herbaceous drugs, pounding roots & rhizomes or turning wood into chips or shavings.
The procedure is conducted in specialized facilities e.g. Soxhlet-type extractor.
SOLVENT EXTRACTIONThe solvent selection is influenced by technical &
economical factors
- Selectivity (being a good solvent for the specific constituents).- Stability (chemical inertness)
- Boiling point should not be so high that the solvent can be completely eliminated; nor too low, to limit losses & control cost- Handling safety
Solvents most used are aliphatic HC’s – petroleum ether, hexane, propane & liquid butane.
Although benzene is a good solvent, its toxicity increasingly limits is use.
SOLVENT EXTRACTIONAt the end of the procedure, the solvent
contained in the plant material is recovered by steam injection.
Main disadvantages of solvent extraction - Lack of selectivity, many lipophilic
substances may end up in the concretes & render further purification necessary.
- The toxicity of solvents leads to the restrictive regulations regarding their use
- Residues in the final product.
ii. METHODS USING OILS & FATS
These procedures take advantage of the liposolubility of the fragrant components of plants in fats.
a. “Enfleurage” – the plant material is placed in contact with the surface of the fat. Extraction is achieved by
- Cold diffusion into the fat - Digestion – carried out with heat, by immersing
the plant in melted fat (also known as hot enfleurage).
The final product is known as a floral pomade.
METHODS USING OILS & FATS
b. PNEUMATIC METHOD: similar in principle to the enfleurage process.
It involves the passage of a current of hot air through the flowers.
The air, laden with suspended (extracted) volatile oil, is then passed through a spray of melted fat in which the volatile oil is absorbed.
iii. EXTRACTION BY SUPERCRITICAL GASSES
Beyond its critical point, a fluid can have the density of a liquid & the viscosity of a gas therefore diffuses well through solids, resulting in a good solvent.
CO2 is the main gas usedAdvantages of CO2
- It is a natural product- chemically inert, non-flammable- non-toxic- easy to completely eliminate- selective- readily available- Inexpensive
EXTRACTION BY SUPERCRITICAL GASSES
DISADVANTAGE: Technical constraints- High cost of initial investment
ADVANTAGES:- obtain extracts which are very close in composition to the natural product.- It is possible to adjust the selectivity & viscosity, etc by fine tuning the temperature & pressure- All result in the increase of popularity of this type of method
EXTRACTION BY SUPERCRITICAL GASSES
USESInitially developed to decaffeinate coffees,
prepare hops extracts or to remove nicotine from tobacco, the method is now used to- Prepare spice extracts (ginger, paprika, celery)- Specific flavours (black tea, oak wood smoke)- Plant oils- To produce specified types of a certain product, e.g. thujoneless wormwood oil.
TREATMENTS OF THE OILS
Occasionally it is necessary to decolourize, neutralize or rectify the oils obtained.
i. Steam jet under vacuumAllows for the elimination of smelly or
irritating products, and to obtain a final product of desired “profile”.
ii. Chromatrographic techniquesThis permits a good separation of the
essential oil from non-volatile lipophilic compounds.
VARIABILITY FACTORS OF ESSENTIAL OILS
i. Occurrence of Chemotypes ii. Influence of the vegetative cycleiii. Influence of environmental factorsiv. Influence of preparation method
i. CHEMOTYPESChemical breeds
commonly occur in plants containing volatile oils, e.g. Thyme (Thymus vulgaris) – has 7 different chemotypes, each with slightly different types & amounts of volatile oils.
ii. THE VEGETATIVE CYCLE
Proportions of the different constituents of a volatile oil may vary greatly throughout its development. Wide ranges are commonly found in fennel, carrot and coriander (linalool is higher in ripe fruit than unripe fruit). Mentha (peppermint) is also greatly affected by the vegetative cycle.
iii. ENVIRONMENTAL FACTORS
Temperature, humidity, duration of daylight (radiation), and wind patterns all have a direct influence on volatile oil content, especially in those herbs that have superficial histological storage structures (e.g. glandular trichomes). When the localization is deeper, the oil quality is more constant.
ENVIRONMENTAL FACTORS
e.g. Peppermint: long days & temperate nights higher yields of oil & menthofuran. Cold nights lead to an increase in menthol.
Laurus nobilis (Bay) [volatile oil] is greater in the southern hemisphere than the northern.
Citrus: higher temperatures = higher oil content.
ENVIRONMENTAL FACTORS
Cultivation practices also play an important factor to the yield & quality of the final product.
Fertilization and the amounts of N, P and K have been studied for various species.
The watering regiment also plays an important role.
PREPARATION METHODBecause of the volatile nature
of the constituents of essential oils, the composition of the product obtained by steam distillation is often different from the constituents originally found in the secretory organs of the plant.
During steam distillation, the water, acidity and tempereature may induce hydrolysis of the esters. Rearrangements, isomerizations, racemiazations, oxidations and other reactions also occur, all of which change the composition.
GINGER: Zingiber officinale
• Definition: Ginger is the peeled or unpeeled rhizome of Zingiber officinale (Zingiberaceae).
• Common Names: Jamaican ginger, Ginger
Zingiber officinalis - GingerGEOGRAPHICAL
SOURCES• Jamaica• China• India Africa
HISTORYCultivated in India from
the earliest times. Used by Greeks and Romans and was a common article of commerce in the European Middle Ages.
CULTIVATION & PREPARATION• Grows well in subtropical
temperatures with high rainfall.
• Grown by vegetative means.
• Mulching or is necessary as the plant rapidly exhausts minerals from the soil.
• When the stems wither, the rhizomes are ready for collection.
• Dried.
MACROSCOPICAL FEATURES• Scraped/peeled herb has
little resemblance to the fresh herb (loss in weight & shrinkage).
• Occurs in branched pieces “hands” or “races”.
• Buds• No cork• Aromatic odour & pungent
taste.• Unscraped rhizome:
resembles scraped herb – • Covered with cork
(brownish layers)
MICROSCOPICAL FEATURES
• Cork cells – high starch content
• Cork cells are absent in the scraped drug.
• Outer zone of flattened parenchyma & inner zone of normal parenchyma.
• Oil cells scattered in the cortex.
Zingiber officinale - CONSTITUENTS
• Volatile oils (1 – 2%)– Camphene– Cineole– Citral– Borneol
• Gingerol – pungent component – Anti-inflammatory• Shogaols – increases bile secretion
• Sesquiterpene HC’s– Zingiberene & Zingiberol (Sesquiterpene alcohol)
• Resins• Starch • Mucilage
Zingiber officinale• VARIETIES
– Chinese Ginger – sliced– African ginger – darker (cortex
is grey – black in colour); lacks the odour but more pungent than Jamaican herb.
• ALLIED DRUGS– Japanese ginger – Z. mioga– Preserved ginger – undried
rhizomes preserved by boiling in syrup.
• ADULTERANTS– Spent ginger– Vegetable adulterants (detected
with microscopical examination).
USES & ACTIONSACTIONS• Carminative• Stimulant• Anti-emetic• Anti-bacterial & Anti-fungal• Sesquiterpene lactones – Anti-
ulcer• Gingerol – pungent component
– Anti-inflammatory• Shogaols– increases bile
secretion & enhanced GIT activity
USES• Motion Sickness• Morning Sickness
CARDAMOM FRUIT & OIL
DEFINITION: Cardamom consists of the dried, nearly dried ripe fruits of Elettaria cardamomum var miniscula (Zingiberaceae).
PARTS USED: Seeds (should be kept in the fruit until ready to be used – Prevents loss of volatile oils).
(3RD most expensive spice).
Elettaria cardamomum • GEOGRAPHICAL
SOURCES– Sri Lanka– India– Guatemala
• HISTORY– Traditional Indian
ceremonies
PRODUCTION, COLLECTION & PREPARATION
• Mainly obtained from cultivated plants (propagated by seedlings or vegetatively [problematic due to virus infection]).
• Capsules on the same plant ripen at different times – important to collect them before they split.
COLLECTION & PREPARATION
• Fruits are dried slowly (outdoors or indoors).
• Too rapid drying – capsules split & shed seeds
• Calyx at the apex of the stalk and the stalk at the base may be removed.
• Fruits are graded with a sift into ‘longs’, ‘mediums’, ‘shorts’ & ‘tiny’.
• If they have been sulphur – bleached (improved colour), it will be aired outdoors before packed for transport.
MACROSCOPICAL FEATURES• Plant is reed-like - > 4 m, with long leaves
growing from the rhizome.• Fruits – capsular: inferior, ovoid, 1-2 cm
long.• Apex: shortly beaked & shows floral
remains.• Base: rounded & shows the remain of a
stalk.• Internally the capsule is 3-celled; each
cell contains x2 row of seeds.• Each seed: Slightly angular, 4mm long &
3 mm broad.• Colour: dark red-brown (fully ripe seeds)
paler in unripe seeds.• Strong, pleasant, aromatic odour• Pungent taste
MICROSCOPICAL FEATURES
• Oil cells• Predominant
Parenchyma (yellow colour)
• Cells containing silica
• Starch grains
VARIETIES & ADULTERANTS
• ADULTERATION– Powdered drug adulterated with the fruit
pericarp (powdered).
• ALLIED HERBS– Official variety – E. cardamomum var
miniscula– Other: E. cardamomum var major (more
elongated & sometimes 4 cm long with dark brown pericarps)
– Amomum aromaticum (Bengal cardamom)– Amomum subulatum (Nepal cardamom)– Amomum cardamomum (Java cardamom)
CHEMICAL CONSTITUENTS
• 2.8 – 6.2 % volatile oil• Abundant starch (up to 50%)• Fixed oil (1 – 10%)• Calcium oxalate
Elettaria: ACTIONS & USES
• Flavouring agent (curries & biscuits)
• Liqueur manufacture
• Small amount is used for pharmaceutical manufacture (Compound Tincture of Cardamom).
CINNAMON: Cinnamomum zeylanicum
• DEFINITION: Cinnamon is the dried bark of Cinnamomum zeylanicum (Lauraceae).
• GEOGRAPHICAL SOURCESCultivated in Sri Lanka, South India, Seychelles, Madagascar, Martinique, Cayenne, Jamaica & Brazil.
CULTIVATION, COLLECTION & PREPARATION
Grown from seedCut down when 2-3
years old.After 5-6 shoots grow
from the stump (18 months), shoots are harvested, trimmed and fermented.
Bark is removed.Peeled bark is then
stretched over a suitable stick
Outer cortex is removed.
PREPARATION OF Cinnamomum
Individually scraped barks are placed inside each other.
Compound quills are dried on wooden frames in the open air without exposure to direct sunlight.
Sorted into grades.
MACROSCOPICAL FEATURESNormally received in shorter
lengths known as ‘cigar lengths’.
Consists of a single or double compound quill about 6-10 mm diameter of varying length.
Thickness of the quill varies according to grade (good quality: Not > 0.5mm), bark: 10-40mm.
External surface: is yellow-brown, shining, wavy lines (pericycle fibres) and occasional scars & holes (leave/twig positions).
Inner surface: darker, longitudinally striated.
Odour: fragrant Taste: Warm, sweet & aromatic
MICROSCOPICAL FEATURES• Transverse: absence of epidermis &
cork• Sclereids (thickened lignified pitted
walls)• Secondary phloem is composed of
phloem parenchyma containing oil & mucilage cells, phloem fibres & medullary rays.
• Some phloem parenchyma contain tannins.
• Secretion cells: volatile oils and mucilage
• Calcium oxalates
Cinnamomum - CONSTITUENTS
• Volatile oils (at least 1.2 %)
• Phlobaphenes• Mucilage• Calcium Oxalate• Starch
CINNAMON OIL – ADULTERATION & ALLIED
HERBSAdulterants• Cinnamon Leaf Oil• Oil of Cassia
Allied Herbs• Cayenne Cinnamon – C. zeylanicum grown
in Brazil – not used in Britain• C. loureirii – from Vietnam – Closely
resembles C. cassia
Cinnamomum zeylanicum - USES
Flavouring agentMild astringent
Oil: CarminativeGermicide
LEMON PEEL Definition: Dried
lemon (Limonis Cortex) peel is obtained from the fruit of Citrus limon (Rutaceae).
Botanical Description:Small tree, growing to
3-5 m in height.
Geographical SourcesMediterranean Regions
Limonis Cortex – COLLECTION & PREPARATION
Lemons are collected in January, August & November, before the green colour changes to yellow.
The smaller fruit, which would not be sold on the produce market, are used in the preparation of oil of lemon - the peel is removed with a sharp knife in the form of a spiral band.
Limonis Cortex – CHARACTERISTICS
Dried lemon peel occurs in spiral bands (2 cm wide; 2-3 mm thick).
The outer surface is rough & yellow; the inner surface is pulpy & white (anatomically similar to that of an orange peel).
Odour: Strong & characteristic
Taste: aromatic & bitter
Limonis Cortex – CONSTITUENTS & USES
CONSTITUENTSShould contain at least
2.5% volatile oilVitamin CHesperidin (Flavonoid)MucilageCalcium Oxalate
USESFlavouring purposes
LEMON OILS - Oleum limonisDefinition: Lemon oil is the oil expressed from the
outer part of the fresh pericarp of the ripe or nearly ripe fruit of Citrus limon (Rutaceae).
BP: oil should be obtained by suitable mechanical means, without the use of heat, from the fresh peel.
Much oil is derived via steam distillation, but this process yields oil of inferior quality.
Distilled oil of lemon is much cheaper than that prepared by expression. Large amounts are used for non-pharmaceutical purposes.
Geographical Sources: Mediterranean, North & South America, Australia &
parts of Africa.
Preparation of Lemon Oilsi. Hand MethodsNo longer applicable
to pharmaceutical oils
Production of Lemon Oilsii. Machine ProcessesQuality is inferior to the best hand-pressed oils.Machines are designed to release oils from the peel via
puncture, rasting or cutting and by imitating the gentle squeezing action of the sponge method. (Superiority of the sponge method is due to the fact that there is no contact between the oil & the inner white part of the skin.
The newer machines extract oil more completely than the older ones and give a higher yeild
iii. Distilled OilsAlthough not official, some lemon oils are produced by
distillation, mainly from the residue of the expression processes. It is much cheaper than hand-pressed or machine-made oil.
Oleum limonis - CONSTITUENTS
Terpenes – mainly limoneneSesquiterpenesAldehydes (Citral & Citronella)Esters
Lemon oil has a tendency to resinify and should be protected from the action of air & light as much as possible.
Oleum limonis – ADULTATION & USES
ADULTERATIONOil of turpentineTerpenes from
‘terpeneless oil of lemon’
Distilled oil of lemonOil of lemon-grass
USESPerfumeryFlavouring
TERPENELESS LEMON OIL
Definition: Oil prepared by concentrating lemon oil in vacuum until most of the terpenes have been removed, or by solvent partition. The concentrate is a terpeneless oil, which has a citral content of 40-50 %.
It is equal in flavouring to 10-15 times its volume of lemon oil
BUCHU – Agathosma betulina
Agathosma betulina – CONSTITUENS & USES
CONSTITUENTSVolatile oils• Pulegone• Menthone & isomenthone• limoneneDiosminMucilageResinCalcium oxalatesBuchu camphor – Responsible for the diuretic action
USES/ACTIONSDiureticUrinary Tract Anti-Septic – Used for UTI’s
NUTMEG & NUTMEG OILDefinition: Nutmeg is
the dried kernel of the seed of Myristica fragrans (Myristicaceae).
Geographical SourcesIndigenous to the
Molucca Islands (Spice Islands)
Cultivated in Indonesia, Malaysia & the West Indies.
NUTMEG – Myristica fragrans
HISTORYFirst Introduced to the
Europeans by the Arabs.
Portuguese lost control of the spice trade to the Dutch, who maintained complete monopoly by destroying all trees in the neighbouring islands & preventing the export of living seeds.
CULTIVATION, COLLECTION & PREPARATION
Trees can be grown from fresh seed gown in the shell. The seeds germinate after about 5 weeks. When the plants are 6 months old, they are transplanted to the fields.
Nutmegs are dried in the shells (process differs according to local conditions). Normally they are dried in the sun & covered at night & rainy weather. They can also be dried in the oven or over low flames.
When completely dried, the kernel rattles in the testa, which is then cracked & the nutmeg extracted.
MACROSCOPICAL FEATURES
Nutmeg trees are evergreen, growing up to 20 m in height.
Nutmegs are oval, 2-3 cm long & 2 cm broad.
If not heavily limed, the surface is a brown or grey brown in colour.
Odour: Strong & aromatic
Taste: Pungent and slightly bitter.
MICROSCOPICAL FEATURES
Potassium acid tartrate crystals
Parenchym with thin brown walls
Oval oil cellsFeathery crystals of
fatFew tannin cells
(containing tannin & starch)
NUTMEG – ALLIED HERBSPapua nutmegs – from M. argentea (New Guinea) – little odour & a disagreeable taste.
Bombay nutmegs – M. malabarica (India) – lack the characteristic odour of the genuine herb.
NUTMEG OILNutmeg oil is distilled from
the kernels of Myristica fragrans.
CONSTITUENTSPineneSabineneCampheneDipenteneSafroleEugenol & eugenol
derivativesMyristicin – a benzene: toxic
to humans (large does of nutmeg or nutmeg oil may cause convulsions).
MACECommon mace or
Banda mace consists of the dried arillus or arillode of M. fragrans.
Description: bright red colour & lacks in aroma.
MACE – CONSTITUENTS & USES
CONSTITUENTS Volatile oils (similar to
that of nutmeg) – eugenol derivatives are the main active constituents – responsible for the anti-bacterial effects.
Also has 2 anti-microbial resorcinols (Malabaricone B and C)
Nutmegs, maces & their oils, are all used for
• Carminatives• Flavouring• Infantile Diarrhoea
(Tea of nutmeg – Ayurveda).
CLOVEDEFINITION: Cloves
are the dried flower buds of Syzygium aromaticum (Eugenia caryophyllus), (Myrtaceaea).
Geographical SourcesMolucca or Clove
Islands, Zanzibar, Pemba, Madagascar, Indonesia & Brazil.
HISTORY OF CLOVECloves were used in China
as early as 266 BC, and by the 4th century, they were known in Europe, although very expensive.
Same as with nutmeg, the Dutch also destroyed all trees from surrounding native islands to secure a monopoly, and cultivated them only in a small group of islands.
In 1770, the French managed to introduce clove trees to Mauritius, and started cultivating them there, as well as in Zanzibar, Penang and Sumatra.
COLLECTION & PREPARATIONThe flower buds are
collected when the lower part turns green-crimson. The cloves are dried in the open air on mats & separated from their peduncles (forming clove stalks which are also sold commercially).
If left on the tree for too long, the buds open & the petals fall, leaving “brown cloves”. Later the fruits (“mother cloves”) are produced.
MACROSCOPICAL FEATURES
Cloves are 10-17.5 mm long.
The head consists of 4 slightly projecting calyx teeth, 4 membranous petals and numerous incurved stamens around a large style.
Odour: Spicy & Pungent
Taste: Aromatic
MICROSCOPICAL FEATURES
Heavy cuticularized epidermis Numerous oil cells (shizolysigenous)Calcium oxalates (cluster crystals &
prisms)Stomata (epidermis of sepals)Starch (Fruit – “mother cloves”)Lignified sclereids
CONSTITUENTS14-21% Volatile oils• Mainly eugenol & isoeugenol• Sitosterol• Stigmasterol• Campesterol
TanninsTriterpene acids & estersGlycosides
USES OF CLOVEStimulant aromaticSpiceFor the preparation
of volatile oilSesquiterpenes:
potential anti-carcinogenic compounds
CLOVE OILOil distilled in
Europe and the US normally does not need purification, while oil distilled in other areas (e.g. Madagascar) does. After purification the oil is sold with varying eugenol contents.
Oil of cloves is yellow or colourless, is slightly heavier than water.
CLOVE OIL - CONSTITUENTS
Volatile oils – mainly eugenol & acetyleugenol
Sesquiterpenes (α and β caryophyllenes)
Oil of clove – like other volatile/essential oils – should be stored in a well-fitted, air-tight container, & should be protected from light & heat.
CLOVE OIL - USESAnti-septicAromaticStimulantFlavouring Agent
EUCALYPTUS LEAFDEFINTION:
Eucalyptus leaf consists of the whole or cut dried leaves of the older branches of Eucalyptus globulus, (Myrtaceae).
GEOGRAPHICAL SOURCES
Portugal, SA, Spain, China, Brazil, Australia, India & Paraguay.
Eucalyptus - DESCRIPTIONMACROSCOPICAL• Older dried leaves are
grey-brown & have lateral veins. Secretory oil cells are visible in leaves held to the light.
MICROSCOPIC• Epidermal cells have a
thick cuticle. • Anisocytic stomata• Mesophyll has
schizogenous oil glands
• Calcium oxalate crystals: Prisms & Cluster crystals
Eucalyptus - CONSTITUENTS
Volatile Oil (at least 2 %)
sesquiterpene - Anti-bacterial action against oral pathogens.
EUCALYPTUS OILOil of eucalyptus is distilled from the fresh
leaves of various species of Eucalyptus and rectified. They are produced in the same countries which produce the dry herb.
Only a certain amount of species produce oil suitable for medicinal use – the main criteria is a high cineole content and low amounts of phellandrene and aldehydes.
Suitable oils are obtained from E. polybractea, E. smithii, E. globulus and E. australiana.
CHARACTERISTICS & CONSTITUENTS
CHARACTERISTICSColourless or pale
yellow liquidAromatic &
camphoraceous in odour.
Pungent & camphoraceous in taste, which is followed by a sensation of cold.
CONSTITUENTS At least 70 volatile oils
(mainly cineole).
EUCALYPTUS OIL - USESAlleviating the
symptoms of nasopharyngeal infections
Treating coughsDecongestant.
Official preparationsMixtures, inhalations,
lozenges and pastilles; also applied externally as ointments and liniments.
FENNELDEFINITION: Fennel
consists of the dried ripe fruits of Foeniculum vulgare (Umbelliferae).
GEOGRAPHICAL SOURCESEurope, India, China & Egypt. Mediterranean origin.
ACTIVE CONSTITUENTS
1-4 % Volatile oil• trans-anethole• Antethole• Estragole• FenchoneFlavonoidsCoumarinsGlycosides
ACTIONS & USESACTIONS• Carminative• Expectorant• Aromatic
- All due to anethole (and fenchone)
USESFlatulenceDyspepsiaChronic coughs &
catarrh
Foeniculum vulgare
Foeniculum vulgare – USESCulinary purposesUsed in medicine as
a flavouringCarminative
CARAWAY & CARAWAY OILDEFINITION: Caraway
consists of the dried, ripe fruits of Caram carvi (Umbelliferae).
GEOGRAPHICAL SOURCES
Wild & Cultivated in Central & Northern Europe, Holland, Denmark, Germany, Russia, Finland, Poland, Hungary, Britain, Egypt, Morocco, Australia & China
MACROSCOPICAL FEATURES
A biennial herb growing up to 1 m in height.
Herb: Normally consists of mericarps separated from the pedicels. Fruits are slightly curved, brown & glabrous.
Size: 4-7 mm long, 1-3 mm wide
Often the stigma & style are still attached.
Characteristic aromatic odour & taste
MICROSCOPICAL FEATURES
Pitted sclerenchymasecretory canalsDark, red-brown
cells containing a pale yellow or colourless oleoresin
Thick cellulose wallsCalcium oxalate
crystals
ACTIVE CONSTITUENTS1-7 % Volatile oils• Carvone• Limonene• Carveole8-20 % Fixed oilsProteinsCalcium oxalatesColouring matterResin
CORIANDER & CORIANDER OIL
DEFINITION: Coriander is the dried, nearly ripe fruit of Coriandrum sativum (Umbelliferae).
GEOGRAPHICAL SOURCES
Indigenous to Italy. Also cultivated in Holland, Central & Eastern Europe, Mediterranean (Morocco, Malta & Egypt), China, India & Bagladesh.
MACROSCOPICAL FEATURESAnnual herb growing
0.7 m in height with white or pink flowers.
Drug: Normally consists of whole cremocarps – straw yellow & 2-4 mm in diameter when ripe.
Considerable variation occurs (e.g. Indian variety > oval).
Apex has 2 styles.Fruits have an aromatic
odour & spicy taste.Unripe plant:
unpleasant mousy odour same odour oil has when made from unripe fruit.
MICROSCOPICAL FEATURES
Outer pericarp: stomata & calcium oxalte prisms.
Thick sclerenchymaTesta:= brown
flattened cellsEndosperm is curved
& consists of parenchymous cells containing fixed oils.
ACTIVE CONSTITUENTS1.8 % Volatile oils• Linalool/coriandrol• Pinene• Terpinene• Limonene• Cymene• Non-linalool alchols & estersFlavonoidsCoumarinsPhenolic acidsHigh fat content (16-28%)Protein (11-17%)
Coriandrum sativum - USESDomestic purposes
(cooking - curries)Pharmaceutically:
flavouring agent & Carminative
PEPPERMINT & PEPPERMINT OIL
DEFINITION: Peppermint is the dried leaves of Mentha piperita (Labiate). It should contain at least 1.2 % volatile oil.
GEOGRAPHICAL SOURCES:Europe & America
MACROSCOPICAL FEATURESAll mints have a square
stem & creeping rhizome.
Black mint, which is the most commonly cultivated variety in England, has purple stems and dark green petiolate leaves tinged with purple. Leaf blades are 3-9 cm long with a grooved petiolate up to 1 cm long.
Pinnate venation. Glandular trichomes:
bright yellow points (hand lens)
Small purple flowers appear in late summer.
MICROSCOPIC FEATURESDiacytic stomataMulticellular
clothing trichomes2 types of glandular
trichomes (one with a unicellar head; with a multicellular head).
Calcium oxalate is absent.
Oleum MenthaeOil of peppermint is
obtained from Mentha piperita via steam distillation using the flowering tops.
Oil should contain at least 44 % menthol, 15-32 & menthone and 4.5-10 % menthyl acetate.
Oleum Menthae - CONSTITUENTS
MentholMenthone & isomenthoneMenthyl acetateLimoneneCineoleMenthofuranPulegoneCineole
OIL COMPOSITION: greatly influenced by genetic factors & seasonal variation.
PEPPERMINT & PEPPERMINT OIL USES
OIL: anti-bacterial, cooling, carminative
HERB: Carminative
Resins and resins combination
Resins and resins combination
• The term ‘resin’ is applied to more or less solid, amorphous products of complex chemical nature.
• On heating they soften and finally melt.
• They are insoluble in water and usually insoluble in petroleum ether but dissolve more or less completely in alcohol, chloroform and ether.
Chemical composition
• Chemically, resins are complex mixtures of resin acids, resin alcohols (resinols), resin phenols (resinotannols), esters and chemically inert compounds known as resenes.
• Resins are often associated with volatile oils (oleoresins), with gums (gum-resins) or with oil and gum (oleo-gum-resins).
• Resins may also be combined in a glycosidal manner with sugars.
• Resins burn with a characteristic, smoky flame.
Balsams• Balsams are resinous mixtures that
contain large proportions of cinnamic acid, benzoic acid or both or esters of these acids.
• The term “balsam” is often wrongly applied to oleoresins and should be reserved for such substances as balsam of Peru, balsam of Tolu and storax, which contain a high proportion of aromatic balsamic acids.
Preparation of resins• Two general classes of resinous
substances are recognized and this classification is based on the method used in preparing them:
1. Natural resins, occur as exudates from plants, produced normally or as result of pathogenic conditions, as for example by artificial punctures e.g. mastic; or deep cuts in the wood of the plant e.g. turpentine, or by hammering and scorching, e.g. balsam of Peru.
2. Prepared resins; are obtained by different methods. The drug containing resins is powdered and extracted with alcohol till exhaustion. The Concentrated alcoholic extract is either evaporated, or poured into water and the precipitated resin is collected, washed and carefully dried. In the preparation of oleoresins; ether or acetone having lower boiling point are used. The volatile oil portion is removed through distillation. When the resin occurs associated with gum (gum-resins), the resin is extracted with alcohol leaving the gum insoluble.
Classification of resins• Resins are classified in three different
ways:1. Taxonomical classification, i.e. according
to botanical origin, e.g. Berberidaceae resins.2. Classification according to predominating
chemical constituent; e.g. acid resins, resene resins, glycosidal resins; etc.
3. Resins may be classified according to the portion of the main constituents of the resin or resin combination; e.g. resins, oleoresins, oleogumresins, balsams.
Examples of resins and resins combination
• Resins: colophony, cannabis.
• Oleoresins: copaiba, ginger.
• Oleo-gum-resins: asafoetida, myrrh.
• Balsams: balsam of Tolu, balsam of
Peru.