Pcog and plant chemistry review

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.


• 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:


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.


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)


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.


• 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


• Commonwealth Period - extension of surveys to

regions not previously explored- clinical and chemical

investigations were made though in a limited scale


• 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


• Immediate Post World War II Period

- First major exhaustive work on medicinal plants by a Filipino - Quisumbing’s Medicinal Plants of

the Philippines, 1951


• 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


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


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


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


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


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


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


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


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


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


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


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


5. Packaging6. Storage

- to prevent insect attacka. simplest methodb. fumigationc. add a drop of preservative

7. Preservation


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 evaluationuse 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


AVOCADO

Persea americana


BALANOY

Ocimum basilicum


BALIMBING

Averrhoa carambola


BANANA

Musa paradisiaca


CHICHIRIKA

Catharanthus roseus


CARROTS

Daucus carota

Important Scientific NamesCHICO

Achras zapota


COTTON

Gossypium hirsutum


DALANGHITA

Citrus nobilis


DAMONG MARIA

Artemisia vulgaris


DRAGON FRUIT

Hylocereus undatus

Important Scientific NamesDUHAT

Syzygium cumini

Important Scientific NamesGUGO

Entada phaseoloides

Important Scientific NamesIKMO

Piper betle


IPIL-IPIL

Leucaena leucocephala


KALAMANSI

Citrus microcarpa

Important Scientific NamesKASOY

Anacardium occidentale


LABANOS

Raphanus sativus


KAMIAS

Averrhoa bilimbi


KANGKONG

Ipomea aquatica


JACKFRUIT

Artocarpus heterophyllus


LANSONES

Lansium domesticum

Important Scientific NamesLEMON

Citrus limon

Important Scientific NamesLINGA

Sesamum indicum

Important Scientific NamesLUYA

Zingiber officinale

Important Scientific NamesCORN

Zea mays


MAKABUHAY

Tinospora rumphi / Tinospora crispa


MAKAHIYA

Mimosa pudica


MALUNGGAY

Moringa oleifera


MANGOSTEEN

Garcinia mangostana

Important Scientific NamesMORAS

Vetiveria zizanioides / Andropogon zizanioides

Important Scientific NamesNIYOG

Cocos nucifera


NONI/APATOT

Morinda citrifolia


ORANGE

Citrus aurantium


PAKWAN

Citrulus vulgaris


POTATO

Solanum tuberosum

Important Scientific NamesPATOLA

Lufa acutangula


PINEAPPLE

Ananas comosus


SAMPALOK

Tamarindus indica


SIBUYAS

Tamarindus indica


SILI

Capsicum annuum


SQUASH

Cucurbita maxima

Important Scientific NamesSUHA

Citrus grandis / Citrus maxima


EGGPLANT

Solanum melongena


TALUMPUNAY

Datura metel


TANGLAD

Cymbopogon citratus


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


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


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.


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 .

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

http://www.uni-graz.at/~katzer/engl/spice_photo.html


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


• 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.


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.


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


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

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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).


Wild & Cultivated in Central & Northern Europe, Holland, Denmark, Germany, Russia, Finland, Poland, Hungary, Britain, Egypt, Morocco, Australia & China


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


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).


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.


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.

Pcog and plant chemistry review

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