INTRODUCTION TO GBPP TEKNOLOGI MINYAK ATSIRI DAN FITOKIMIA
INTRODUCTION TO
GBPP TEKNOLOGI MINYAK ATSIRI DAN FITOKIMIA Ø Pengenalan minyak atsiri Pemanfaatan, jenis, definisi, komponen atsiri Ø Penggolongan senyawa dalam minyak atsiri Terpenoid, benzen, rantai lurus, senyawa N, S Ø Reaksi senyawa minyak atsiri Esterifikasi, reduksi, oksidasi, hidrolisis, adisi
Ø Isolasi/Ekstraksi dengan metode penyulingan Prinsip, tipe kondensor, peristiwa, jenis penyulingan, keunggulan, kerusakan, faktor yang mempengaruhi, alat dan proses penyulingan Ø Isolasi minyak atsiri dengan metode adsorbsi Prinsip, faktor yang mempengaruhi daya adsorbsi, rendemen dan mutu, pembuatan lemak, syarat bunga, proses, cara adsorbsi enfleurasi dan maserasi Ø Isolasi minyak atsiri dengan metode solvent extraction prinsip, deret eutropik pelarut, syarat pelarut, skema proses, daerah kritis penyebab loss pelarut
Ø Isolasi minyak atsiri dengan metode press/kempa Prinsip dasar, syarat bahan yang dikempa Ø Analisis sifat fisikokimia Bilangan iod, putaran optik, kelarutan dalam etanol, bilangan asam, bilangan ester, analisis komponen utama, analisis GC
Volatile Oils, Essential oils, Ethereal oils Ø Oily liquids, which are entirely or almost entirely volatile without decomposition Ø Plant products, giving the odors and tastes characteristic of the particular plant, thus possessing the essence. Ø Ether like in their volatility.
ESSENTIAL/VOLATILE OILS All 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).
WORLD ESSENTIAL OIL TRADE World total essential oil value >USD 4 billion, average growth/yr >5% Ø Indonesian export >USD 120 million Ø Worls essential oil trade >300 items Ø Indonesia >40 items, commercialized or potentially Ø
World Major Essential Oils approx. volume for 2007 Essential Oil Production (MT) Major Source Derivative Prod. Orange 51, 000 Brasil, USA High Cornmint 32, 000 India, China High Lemon 9, 200 Argentine, Spain High Eucalyptus 4, 000 China, India Medium Peppermint 3, 300 USA, India Medium Citronella 1, 800 China, Indonesia Medium Clove Leaf 1, 800 Indonesia, Madagascar High Sassafras 1, 800 China High Lime 1, 800 Mexico, Low Lavandin 1, 300 France, Spain Low Patchouli 1, 200 Indonesia, China Low Brian Lawrence- Perfumer & Flavourist v. 34 January 2009
INDONESIAN AROMATIC PLANTS Clove Nutmeg Benzoin Cinnamo n Citronella Clove Nutmeg Patchouli Pepper Cajeput Clove Nutmeg Massoi a Cajeput Cananga Citronella Clove Cubeb Galanga Ginger Kaffir Lime Patchouli Clove Sandalwood Indonesia is #1 grower of Cajeput, Cananga, Clove, Cubeb, Galanga, Kaffir lime, Massoia, Nutmeg, Patchouli Indonesia is # 2 -5 grower of Benzoin, Cinnamon, Ginger, Pepper Sandalwood, Vetiver
Indonesian Essential Oil Production 2009 Ø Ø Ø Total production 5000 -6000 tons, USD 125 -150 mill 80% of export comes from 3 main oils 60% essential oil, 30% derivative products for export, 10% industry (food, cosmetic, consumer goods, pharmacy) No Items Output (MT) Remarks 1 Clove/Stem Leaf 1, 900 -2, 000 2 Patchouli 3 Nutmeg 350 -400 4 Citronella 300 -400 Domestic > Export 5 Cajeput 200 -300 Mostly for domestic 7 Gurjun 50 -60 6 Vetiver 25 -30 8 Cananga 12 -15 9 Massoia 12 -13 10 Eaglewood (aetoxylon sympetalum) 10 -12 11 Lajagoa (alpina malaccensis) 3 -4 12 Cubeb 2 -3 13 Sandalwood 1 -2 14 Kaffir Lime Leaf 1 -2 15 Agarwood Mostly for derivatives 900 -1, 000 0. 1 -0. 2
FUNCTION OF VOLATILE OILS In 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.
Function Ø Attracting (help polination) or repelling insects Ø Protection from heat or cold Ø As antibacterial agents Ø Uses : Pharmacy, aromatherapy, Perfumery, Food technology
LOCALIZATION Synthesis & 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)
Localization Usually in specialized histological structures
Distribution In higher plants, different families as: Rutaceae, Myrtaceae, Lamiaceae (Labiatae), Lauraceae Ø Accumulate in all types of vegetable organs: Flowers (rose), Leaves (eucalyptus), Barks (cinnamon) Ø
Woods (Sandalwood) Stem bark (cinnamon) Rhizomes (ginger), Fruits (star anise), v Roots (vitiver. ) Seeds (nutmeg). May occur associated with other constituents: gums (oleogums), resins (oleoresins) gums & resins (oleogumresins)
An essential oil is a concentrated hydrophobic liquid containing volatile aroma compounds from plants. Essential oils are also known as volatile oils, ethereal oils or aetherolea Essential oils are derived from various sections of plants. Berries • Allspice • Juniper Seeds • Almond • Anise • Celery • Cumin • Nutmeg oil Bark • Cassia • Cinnamon • Sassafras Wood • Camphor • Cedar • Rosewood • Sandalwood • Agarwood Rhizome • Galangal • Ginger Leaves • Basil • Bay leaf • Cinnamon • Common sage • Eucalyptus • Lemon grass • Melaleuca • Oregano • Patchouli • Peppermint • Pine • Rosemary • Spearmint • Tea tree • Thyme • Wintergreen Resin • Frankincense • Myrrh Flowers • Cannabis • Chamomile • Clary sage • Clove • Scented geranium • Hops • Hyssop • Jasmine • Lavender • Manuka • Marjoram • Orange • Rose • Ylang-ylang Peel • Bergamot • Grapefruit • Lemon • Lime • Orange • Tangerine Root • Valerian • Vetiver
Decomposition In some cases the essential oils don’t pre-exist but formed by decomposition of a glycoside -Benzaldehyde (amygdalin) in bitter almond -Allyl isothiocyanate(sinigrin) in black mustard
USES OF VOLATILE OILS Ø Ø Ø Ø 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 distillation ii. Expression 4 Main types of volatile oils i. Concretes ii. Pomades iii. Resinoids iv. Absolutes
CONCRETES Prepared 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.
CONCRETES Concretes 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.
POMADES True 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: METHOD A 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.
RESINOIDS Prepared 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)
RESINOIDS Can be viscous liquids, semi-solid or solid. Usually homogeneous mass of noncrystalline character. Uses: in perfumery as fixatives to prolong the effect of a fragrance.
ABSOLUTES Ø Obtained from a concrete, pomade, or a resinoid by alcoholic extraction. Ø The extraction process may be repeated. Ø The ethanol solution is cooled & filtered to eliminate waxes. Ø The ethanol is then removed by distillation. Ø They are usually highly concentrated viscous liquids.
Aromatic material of natural origin Essential Oils obtained by Distillation Oil Aromatic extracts obtained by Expression Solvent Extraction Enfleurage Citrus oil Resinoids Concretes Absolutes Pomades Enfleurage absolutes
Physical properties q Possess characteristic odors q Liquids and volatile at ambient temp. q Soluble in common organic solvents. Sparingly soluble in water, however sufficient to produce aromatic water. q Specific gravity (0. 8 -1. 17), mostly lighter than water (clove and cinnamon are heavier). q Have high refractive index and most of them rotate the plane of polarized light.
Comparison between fixed oils and essential oils Ø Their volatility Ø When smeared on paper Ø Oxidation (resinified, fixed oil rancid) Ø Chemical structure Ø Saponification by KOH (NOT saponify)
CHEMICAL COMPOSITION Volatile 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
VOLATILE OIL COMPOSITION Ø Mixtures of HC’s and oxygenated compounds derived from these HC’s. l l Oil of turpentine – mainly HC’s Oil of Clove – mainly oxygenated compounds EXCEPTION: Oils derived from glycosides (e. g. bitter almond oil & mustard oil). Ø Oxygenated compounds – responsible for the odour/smell of the oil. They are slightly water soluble – Rose water & Orange Ø Water; more alcohol soluble. Most volatile oils are terpenoid. Some aromatic (benzene) derivatives mixed with terpenes. Ø Some compounds are aromatic, but terpenoid in origin (e. g. Thymol – Thyme) Ø
NUTMEG & NUTMEG OIL Definition: Nutmeg is the dried kernel of the seed of Myristica fragrans (Myristicaceae). Geographical Sources Indigenous to the Molucca Islands (Spice Islands) Cultivated in Indonesia, Malaysia & the West Indies.
NUTMEG OIL Nutmeg oil is distilled from the kernels of Myristica fragrans. CONSTITUENTS Pinene Sabinene Camphene Dipentene Safrole Eugenol & eugenol derivatives Myristicin – a benzene: toxic to humans (large does of nutmeg or nutmeg oil may cause convulsions).
MACE – CONSTITUENTS Consists of the dried arillus Used for carminatives, or arillode of M. fragrans. flavouring, infantile diarrhoea (Tea of nutmeg – Ayurveda). Description: bright red colour & lacks in aroma CONSTITUENTS Volatile oils (similar to that of nutmeg) – eugenol derivatives are the main active constituents – responsible for the antibacterial effects. Also has 2 anti-microbial resorcinols (Malabaricone B and C)
CLOVE DEFINITION: Cloves are the dried flower buds of Syzygium aromaticum (Eugenia caryophyllus), (Myrtaceaea). 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 Oil of cloves is yellow or colourless, is slightly heavier than water.
CLOVE OIL - CONSTITUENTS 14 -21% Volatile oils mainly eugenol, isoeugenol, & acetyleugenol Sesquiterpenes(α and β caryophyllenes) Stigmasterol, Campesterol, Tannins Triterpene acids & esters, Glycosides Oil of clove – like other volatile/essential oils – should be stored in a well-fitted, air-tight container, & should be protected from light & heat.
Derivatives of Clove Oil ETHYL ISOEUGENOL METHYL ISOEUGENOL ISOEUGENYL ACETATE VANILLIN PROPENYL GUAETHOL BENZYL ISOEUGENOL CARYOPHYLLENE EUGENYL ACETATE METHYL EUGENOL ISO EUGENOL BENZYL EUGENOL ACETATE DIHYDRO EUGENOL Distillation Fractionation Acetylation EUGENOL Isomerisation Methylation CARYOPHYLLENE CLOVE OILS Hydrogenatio n Oxidation CLOVE BUD/LEAF/STEM Benzylation Ethylation
CINNAMON: Cinnamomum zeylanicum Individually scraped barks are placed inside each other Consists of a single or double compound quill about 6 -10 mm diameter Thickness : good quality: Not > 0. 5 mm, bark: 10 -40 mm. 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
Cinnamomum - CONSTITUENTS • • • Volatile oils (at least 1. 2 %) Phlobaphenes Mucilage Calcium Oxalate Starch
EUCALYPTUS DEFINTION: 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.
CHARACTERISTICS & CONSTITUENTS CHARACTERISTICS Colourless or pale yellow liquid Aromatic & camphoraceous in odour. Pungent & camphoraceous in taste, which is followed by a sensation of cold. CONSTITUENTS At least 70 volatile oils (mainly cineole).
GINGER Scraped/peeled herb has little resemblance to the fresh herb (loss in weight & shrinkage) Ø Cork cells – high starch content Ø Outer zone of flattened parenchyma & inner zone of normal parenchyma. Ø Oil cells scattered in the cortex. Ø
Zingiber officinale - CONSTITUENTS Ø Volatile oils (1 – 2%) l l Camphene Cineole Citral Borneol Gingerol – pungent component – Anti-inflammatory Ø Shogaols – increases bile secretion Ø Sesquiterpene HC’s Ø l Zingiberene & Zingiberol (Sesquiterpene alcohol) Resins Ø Starch Ø Mucilage Ø
LEMON OILS - Oleum limonis Definition: Dried lemon (Limonis Cortex) peel is obtained from the fruit of Citrus limon (Rutaceae). Dried lemon peel occurs in spiral bands (2 cm wide; 23 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
LEMON OILS - Oleum limonis Definition: 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). 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 nonpharmaceutical purposes.
Oleum limonis - CONSTITUENTS Terpenes – mainly limonene Sesquiterpenes Aldehydes (Citral & Citronella) Esters Lemon oil has a tendency to resinify and should be protected from the action of air & light as much as possible. 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
TYPICAL FORMULA OF FRAGRANCE COMPOUND (JASMINE) BENZYL ACETATE 50% 1 -P-METHEN-8 -OL 10% METHYL-2 -AMINOBENZOATE 5% 4 -(2, 5, 6, 6 -TETRAMETHYL-2 -CYCLOHEXEN-1 -YL)-3 -BUTEN-2 -ONE 5% 3 -METHYLBUTYL O-HYDROXYBENZOATE 5% ALPHA-CINNAMALDEHYDE 5% CANANGA OIL 5% PETITGRAIN OIL 5% STYRAX 5% MUSK XILENE 3% RECTIFIED CLOVE LEAF OIL 2% ESSENTIAL OIL in FRAGRANCE COMPOUND: 10 – 25% FRAGRANCE COMPOUND IN SOAP: 1 – 1. 2%, IN EAU de TOILETTE: 6 -8%
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