gcms presentation - natural products
TRANSCRIPT
The Metabolite Map for Identifying
Probabilities and Olfactory Analysis As A Supplement to GCMS
Analysis Murray Hunter
Oxygen
Carbon Dioxide
Water
Nitrates & Mineral Salts
Glycose
Polysaccharides & Disaccharides
Glycolysis
6-Deoxyxylulose
Isoprenoids (terpenoids)
Erythrose 4-phosphate
Pentose Phosphate Pathway
Phosphoenol pyruate
Pyruvate Hydroxy-
Benzoic Acid
Shikimate Pathway
Alkaloids
Phenylpropanoids
Complex Alkaloids
KREBS CYCLE
Acetyl-CoA
Malonyl-CoA
Mevalonic Acid
Complex Isoprenoids (terpenoids) Polyketides
Flavonoids
Complex Flavonoids
Primary Metabolites (in blue) Secondary Metabolites (in red)
Aromatic Amino Acids
Amino Acids & Nucleotides
Photosynthesis
Triglycerides
2. Using CGMS in Forensic Fragrance Construction
3. Using CGMS in Identifying Essential oil constituents
4. Using CGMS in Quality Assurance of Flavours & fragrances
1. Olfactory Evaluation
Essential OilA volatile oil obtained from a wide variety of plant, scrub, and tree species and from various parts of the plant anatomy, such as the roots, rhizomes, wood bark, leaves, stems, fruit, flowers and seeds. Usually extracted by hydro or steam distillation, expression or effleurage - Hunter 1996
Concretes and Absolutes
Volatiles and waxes extracted from plant material with hydrocarbon solvents (usually benzene and hexane) through washing and removal of the volatile solvent with distillation. A waxy aromatic substance remaining is called a concrete. The concrete is washed with alcohol to remove the volatile materials and ethanol removed through vacuum distillation to leave an absolute.
Plant Material
Expressed
Oil
Cold expression of citrus fruits
Terpeneless Oil Terpene Tails
Essential
Oil
Water, water & steam and steam
Distillation
Absolute
Concrete
Solvent Extraction
Washing with ethanol and vacuum distilling
ethanol away
Pomade
Enfleurage
Vacuum distill away the ethanol
Oleoresin
CO2
Extract
CO2 Extraction
The Natural Aromatic Product Family
Olfactory epithelium
• Olfactory mucosa– Mucus!– High in nasal cavity– Site of transduction– Contains olfactory
receptor neurons (ORN)
11
Nose hair: Olfactory cilia• ORN have cilia• Cilia contain olfactory
receptor proteins– Similar to visual
pigment• Transduction
– Odorants bind to ORs– Change shape of
protein– Ion flow across OR– Electricity
TransmissionOlfactory ReceptorsOlfactory Cells line the Olfactory Epithelium which is responsible for olfactionEach cell has cilia where receptor sites are locatedReplaced every monthAxons of the olfactory receptors carry information to the olfactory bulbOlfactory bulb sends axons to several specific parts of the cortex with precise connections From the cortex, information is sent to other areas that control feeding & reproduction
Olfactory DisorderAnosmia: the general lack of olfactionSpecific Anosmia: the inability to smell a specific chemical
13
How many receptor types are there?
• 1000 different kinds of olfactory receptors (OR)• 10 million OR neurons
– 10,000 of each type of OR– Each OR neuron has only one type of receptor– 1000 neuronal chemical detectors– Potential to differentiate between 5,000-10,000 different
odours
Olfactory Bulbs
• An outcropping of the brain
• Its like a snail in your brain!
• Electrical responses in cilia passed through olfactory nerve to OB
The hedonic primacy of olfaction• Sensory and emotional experience• Not the same for vision/audition
– Seeing and feeling more distinct• More intertwined in the chemical senses
– Why?• Orbitofrontal cortex
– Plays multiple roles– Critical for emotional experience– Secondary sensory cortex for olfaction– Also centre of creativity and imagination
Nobel Prize
• October 4, 2004 - Richard Axel and Linda Buck honored with the 2004 Nobel Prize in Physiology or Medicine for pioneering studies that clarify how the olfactory system works.
Top Notes
Middle Notes
Base Notes
The Structure of a Fragrance
Bergamot oil, Rosewood oil (linalool), Linalyl acetate, Neroli oil, Ciste Oil
Rose Oil 5%, Jasmin absolute 4%, Ylang Ylang Oil, Aldehyde C11, C12, Methyl ionone 8%, hydroxycitronellal 10%, Cinamic Alcohol, Styrax. Phenol ethyl alcohol, Phenylacetaldehyde
Vetiveryl acetate, Sandalwood, Isoeugenol, Vanillin 1.5%, Coumarin 15%, Nitromusks 10%
“First Impression” in Perfume. High Volatile Citrus, Fresh, Green notes…..
“ Heart of fragrance”. Intermediate VolaleFloral, Aldehydic notes…..
Basic of fragrance”.(Bottom) Low VolatileWoody, Powdery, Musky …..
Classification of Odours
Spicy
Medicated
Aldehydic
Marine
Coniferous
Minty
Green
Herb -aceous
Fruity
Balsamic
Animalic
Woody
Floral
Agrestic
Curtis & Williams (1994)
Floral Family Broom Sweet, Floral, Herbaecious Carnation Delicate, Floral, CloveCassie Floral, Orange flower, VioletClover Sweet, Honey, Herbaecious, FloralCyclamen Floral, Lily, Lilac, Violet, greenGardenia Floral, Tuberose, Jasmin, Orange flowr, GreenHawthorn Floral, Bitter almond, Bitter, DiffusiveHeliotrope Floral, Almond, Balsamic, FruityHoneysuckle Swet, Floral, Heavy, Orange Flower, Tuberose,
Honey, RoseHyacinth Fresh, Green, Floral, Jasmin, BalsamicJ asmin Sweet, Floral, Heavy, Fruity, HerbaeciousJ onquil Fresh, Floral, Sweet, Heavy, Honey, GreenLilac Fresh, Meadow-Floral, Jasmin, GreenLily Sweet, Heavy, FloralLily of the Valley Floral, Rose, Green, Slightly citrusLime Blossom Floral, Fresh, Lily, Lilac, Orange FlowerMagnolia Floral, Lily, Ylang YlangMimosa Sweet, Floral, Hawthorn, Orange flower, GreenNarcissus Delicate, Fresh, Green, Floral, SweetOrange Flower Floral, Heavy, Animalic, Fresh, Rich, BitterOrris Delicate, Dry, Woody, Somewhat VioletReseda Floral, Green, Anisic, HerbaceousRose Sweet, Floral, Honey, Waxy, Slightly spicy,
FruitySweet Pea Sweet, Delicte, Floral, Orange Flower, Hyacinth,
LilyTuberose Heavy, Floral, Orange Flower, Ylang Ylang,
Caramel, GreenViolet Floral, Powdery, GreenWallflower Floral, somewhat liliacy, bitter almondYlang Ylang Rich, Sweet, Medicated, Floral, Fruity, Clove
Floral Family Descriptions
Woody Family Cedarwood Woody and slightly earthy, with smoky notesHibawood Like cedarwood, but more intensely woody,
Dry, PungentRosewood Woody, Floral, Sweet, Spicy, Delicately FattySandalwood Soft, Sweet, Woody, Slightly Balsamic
Woody Family Descriptions
Animalic Family Amine Fishy notes, AmmoniaCastoreum Warm, Phenolic, Sweet, Somewhat herbaceous,
clean smellingCatty Feline odourCivet Warm, Slightly faecal, MuskyEquine Horse likeFaecal Indolic, skatolicIndolic Lilac, Heavy, Animalic, NaphthalenicMusky Blackberry likeLeather Phenolic, Cresylic, Animalic, Castoreum,
Balsamic
Animalic Family Descriptions
Balsamic Family Cistus Rich, Balsamic, Ambergris, HerbaceousLabdanum Rich, Balsamic, AmbergrisMyrrh Rich, Warm, Balsamic, SpicyOpopanax Warm, Vegetable note, Rich, Balsamic, SpicyPeru Balsam Sweet, Balsamic, Rich, Soft, Vanilla,
Cinnamate, BenzoateStyrax Sweet, Balsamic, CinnamateTolu Balsam Sweet, Balsamic, Cinnamate, VanillaVanilla Soft, Sweet, Powdery, Balsamic
Balsamic Family Descriptions
Herbaceous Family Lavender Fruity, Floral, Herbaceous, Woody, BalsamicRosemary Herbaceous, Resinous, Woody, BalsamicSage Herbaceous, Slightly camphoraceous
Herbaceous Family Descriptions
Agrestic Family Earthy Fresh, Woody, VegetableForest Moist, Fresh, Vegatable, WoodyFungal Mushroom likeGalbanum Sharp, Agrestic, Green, Earthy, ConiferousHay Sweet, Warm, Agrestic, Herbaceous
Agrestic Family Descriptions
Green Family Cress Hyacinth like, GreenCucumber Green like sliced green vegetable pods
Fresh and CleanGrassy Fresh, Green, FruityLeafy Light, Green
Green Family Descriptions
Minty Family Peppermint Fresh, Cool, Mentholitic, Minty, Slightly GreenSpearmint Sweet, Warm, Minty, Herbaceous, GreenMossy Notes Forest, Woody, Phenolic, Green, Somewhat
marine
Minty Family Descriptions
Coniferous Family Description
Coniferous Family Pine Resinous, Balsamic, TerpeniticResinous Forest, Woody, Terpenite, Balsamic
Marine Family Ambergris Marine, Seaweed, Mossy, DryBeachOzonic Fresh, Marine, Slightly SweetSeaweed Marine, Mossy, Amine
Marine Family Descriptions
Aldehydic Family Fatty, Waxy (pleasant in dilution)
Aldehydic Family Descriptions
Medicated Family Camphorous CamphorCineolic Eucalyptus, Cresylic Cresolic, PhenolicEthereol alcoholicMentholic MentholPhenolic PhenolTerpenic monoterpenesThymolic ThymolWintergreen Methyl salicylate
Medicated Family Descriptions
Fruity Family Bergamot Fresh, Lemon, Sweet Orange, Herbaceous,(Citrus Sub-Class) Pepper, Floral
GrapfruitLemonLimeMandarinOrange SweetOrange BitterPithy Orange PeelTangerine
Fruity Family AppleApricotBananaBlackberryBlackcurrentPearPeachPineapplePruneRasberryStrawberryVinous Cognac likeWatermellon
Fruity Family Descriptions
Sub-Class (Citrus)
Spicy Family CeleryCinnamomCloveCorianderCuminFenugreekGingerNutmegPepper
Spicy Family Description
Miscellanious Bitter AlmondNotes Anisic
BenzoateBurntCaramelCinnamateCoconutFattyGeraniumHoneyMetallicNaphthenicNondescriptOilyPatchouliSalicylateSmokySulphorousTobaccoWaxy
Miscellaneous Notes
Light HeavySweet DryFresh StaleWarm CoolSoft Hard
Smooth HarshRich Thin
Delicate Coarse
Odour Characteristics
BitterDifussivePowderyPungentSharp
Tropical
Additional Characteristics
Spicy
Medicated
Aldehydic
Marine
Coniferous
Minty Green
Herb aceous
Fruity
Balsamic
Animalic
Woody
Floral
Agrestic
Fragrance Description Workshop
Perfumer Excellence
Knowledge (vocabulary) of
odorous substances
Knowledge of potential strengths,
weaknesses and applications of
odorous materials
Knowledge of outstanding
fragrance creations within the domain
Practical knowledge & experience
Olfactory sensitivity
Time, patience, perseverance
Interest and passion
Imagination
Knowledge Base Emotion
Cognitive Skill Creativity Tool
Process & Product
Curiosity, enquiry and
experimentation
Apples aren't the same
Sweet, sour, green, red, sharp, fresh, wholesome, etc.
This means different aromatic chemicals play a role in fragrance
1964 – Introduction of Furaneol®
1965 – First publications on isolation of Furaneol®from strawberry and pineapple
O
O OH
O
O OH
1960’s – Nootkatone
First isolated in 1962, it’s importance to citrus flavor was unknown until it’s isolation from grapefruit by Mcleod in 1964.In 1966, Coca-Cola introduced Fresca. By 1970, Nootkatone was GRAS and became a key ingredient in Fresca. Coca-Cola manufactured Nootkatone for many years and soon made it available to the flavor industry.
OO
(+)-Nootkatonestrong grapefruit odor, bitter in taste
(-)-Nootkatoneweak woody (vetiver note); no grapefruit character; virtually no taste
Threshold: 60,000 ppb 800 ppb
1970’s-80’s – Other Furanones
Sotolon (caramel furanone) & Maple furanone identified in cane sugar – powerful caramel maple notes
O
HO
OO
HO
O
Sotolon Maple Furanone (Abhexone)
Threshold: 0.003 ppb 0.00005 ppb
Sotolon – key flavorant of fenugreek, sake, sherry wine
1968 – Pfizer patents Ethyl maltol
O
OH
O
Ethyl maltol (Veltol Plus®) was touted to be about 6Xstronger than maltol and an important substitute for Coumarin. Well, at least it is stronger than maltol.
1975 - Introduction of α-Damascone and β-Damascone1982 – Introduction of Damascenone
1970 – Discovery Damascenone & β-Damascone
OO O
1974 – Thiomenthones identified in Buchu oil
OHS
OHS
Key component for black currant and the “fuzzy” peach skin note
1980 – Patent on Oxane®
1977 - Winter identifies 2-methyl-4-propyl-1,3-oxathiane as a character impact compound in Passionfruit 1984 – Pickenhagen determines that (-)- cis- 2-methyl-4-propyl-1,3-oxathiane is the important diastereomer
O
S
H H
(-)-(2R,4S)-2-methyl-4-propyl-1,3-oxathiane
• Odor: powerful sulfury, tropical fruit• Threshold: 2 ppb
O
S
HH
(+)-(2S,4R)-2-methyl-4-propyl-1,3-oxathiane
• Odor: flat, estery, camphoraceous, floral, less sulfury • Threshold:4 ppb
SH
S
1982 – 1-p-Menthene-8-thiol
Demole identifies 1-p-Menthene-8-thiol as a character impact compound in Grapefruit Juice
Very powerful with an odor threshold of 0.0001 ppb, it alsorequires stabilization as it tends to rapidly cyclize to the thio analog of dihydropinol.
O
O
O
O
O
O
Mintlactone (1983) Dihydromintlactone (1995)Wine lactone (1996)
GRAS No. -- 3764 4032Odor: Vinous, lactonic Minty, coumarinic, Coumarinic, hay,
(coconut) tenacious lactonic, tonkaFlavor: Lactonic, sweet, herbal Coumarinic, fatty, Coumarinic,
herbal lactonic, coconutThreshold*: 0.0000016ppb 0.00012 ppb 0.000039 ppb*In airRef: Frerot, et. al., Flavour Fragr. J., 2002; 17: 218–226; Gaudin, Tetrahedron, 2000, 56: 4769-4776
Coumarinic p-Menthane Lactones
1962 – First publications appear on Methyl Jasmonate & Methyl Dihydrojasmonate
1R,2R-(-)-Z-methyl jasmonate 1S,2S-(+)-Z-methyl jasmonate
4
5
1(R)
2 (R)
3
O
(Z)
CO2CH3
H
H
(S)(S)
O
(Z)
H3CO2C
H
H
(R)(S)
O
(Z)
CO2CH3
H
H
(S)(R)
O
(Z)
H3CO2C
H
H
1R,2S-(+)-Z-methyl epijasmonate 1S,2R-(-)-Z-methyl epijasmonate
Methyl Jasmonate – odorant, insect pheromone, plant growth regulator
Advances in Flavoring Materials
Chirality & Odor - Methyl Jasmonate & Methyl DihydrojasmonateConfiguration Odor Description Odor Threshold (in PPB)Methyl jasmonates1R,2R-(-)- Weak odor >70*1S,2S-(+)- Odorless Odorless1S,2R-(-)-epi- Odorless Odorless1R,2S-(+)-epi- Strong odor; floral, true jasmin-like 3*Ref: T.E. Acree et. al., J.Agric.Food.Chem. 1985Methyl dihydrojasmonates1R,2R-(-)- Floral, sweet, jasminelike 240**1S,2S-(+)- Floral, fatty, cis-jasmone, hay character, 15,360**
tea note, slightly lemon peellike (weak)1S,2R-(-)-epi- Herbal, fatty, tea-like, tobacco, 12,500**
β-damascone, cis-jasmone1R,2S-(+)-epi- Intensely floral, jasmine-like, bright, cis- 15**
jasmone, slightly fatty, woody, β-ionone-like, extremely long lasting
Ref: Werkhoff, P., et. al., Food Reviews International, 2002* detection threshold**recognition threshold
Advances in Flavoring Materials
2001 – Takasago’s Professor Ryoji Noyori wins the 2001 Nobel Prize for Chemistry
HOOH
12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 28.00 30.00 32.00 34.00 36.000
2000000
4000000
6000000
8000000
1e+07
1.2e+07
1.4e+07
1.6e+07
Time-->
•Abundance
GC-MS Analysis of a Meat Flavor
Peak Identified as Furfuryl MercaptanPowerful Coffee Aroma
Peaks are 2-Methyl-2,3-dihydrofuran-3-thiol isomersPowerful meat-like aroma
O
SH
CH3 O
SH
CH3
O
SH
Representative IngredientsNatural : Lemon Oil, Bergamote, Lime….Chemical : Citral, Dihydo Myrcenol….
Representative Fine Fragrance
O de Lancome (1975. Lancome)Bulgari Eau Parfume (1992. Bulgari)CK one (1994. C.Klein)
Eau Savage (1966.C.Dior)
BergamotLemonOrange
Rose JasmineLily of Valley
OakmossAmbergrisCivet
• Citrus notes Citrus + Floral
• Citrus notes
BergamotLemonMandarinDihydro Myrcenol
JasminMuguet
AmberMuskSandalwood
Green
Citrus
Floral
Amber
Woody Musk
• Floral notes Floral + Floral
Representative IngredientsNatural : Jamine Abs, Ylang Ylang, Rose Abs. Tuberose ….Chemical : Hedion, Benzyl Acetate….
Representative Fine Fragrance
Joy (1935. Jean Patou)Diorssimo (1956.C.Dior)Anais Anais (1979. Cacharel)Paris (1983. YSL)Beautiful (1985. E. Lauder)
Green
JasmineRose Ylang YlangVioletMuguet
MuskSandalwoodPowdery
Green
Floral
MuskWoodyPowdery
• Aldehydic notes Floral + Aldehydic
Aldehyd 10MuguetYlang-Ylang
JasmineRoseCarnationAldehyde C-11Aldehyde C-12
VanillaSandalwoodMusk
Floral
Aldehyddic
WoodyPowder
Representative IngredientsNatural : Not available Chemical : Aldehyde C-11, Aldehyde C-12..….
Representative Fine Fragrance
Chanel No. 5 (1921. Chanel)Calandre (1969. 1969. Rabanne)First (1976. Van Cleef & Arpels)
• Spicy notes Floral + Spicy
BergamotYlang Ylang
CarnationJasmineRoseIris
SandalwoodCedarwoodMusk
Floral
Spicy Floral
WoodyMusk
Representative IngredientsNatural : Clove Buds oil, Pepper oil, Cinnamon oil. Carnation……. Chemical : Eugenol, Cinnamic Aldehyde ..….
Representative Fine Fragrance
L’air du Temps (1948. Nina Ricci)Fidji (1966. Guy Laroche)
Egoist (1990. Chanel)
• Chypre notes What is Chypre….?
Citrus Green Aldehyde
Floral (Jasmine, Rose, Ylang…)
WoodyMossyPatchouli
Representative Fine Fragrance
Mitsouko (1919. Guerlain)Miss Dior (1947. Christian Dior)Coco (1984. Chanel)Ysatis (1984. Givenchy)
Representative IngredientsNatural : Oak moss Abs. Vertiver, Patchouli oil Galbanum Cederwood, SandalwoodChemical : Veramoss, Iso E Super..….
BergamotMandarinGalbanumAldehydC-11
JasmineRose Ylang-YlangMuguet
AmberMossyPatchouliMossyWoody
Oriental
CitrusGreenAldehyde
Floral
AmberWoodyMossy
• Chypre notes - Fine Fragrance
• Oriental notes What is Oriental….?
Citrus MandarinLemon
Spicy(cinamon..)Floral
Vanilla Abs.SweetBalsam
Representative IngredientsNatural : Vanilla, Tolu Balsam, Mandarin, Cinnamon Chemical : Vanillin, Galaxolide..….
Representative Fine Fragrance
Shalimar (1925. Guelain)Obsession (1984. Calvin Klein)Opium (1977. YSL)Samsara (1989. Guelain)Jean Paul Gaultier (1993. J.P.Gaultier)
BergamotLavendinCloveSpearmint
MuguetGeraniumCarnation
PowderyMossyCederwood
Herbacious
Floral
WoodyPowdery
• Fougere notes - Fine Fragrance
Biological Screening
Bio-prospecting Literature Review
Consider Crop Reintroduction Consider New Crop Introduction
Identify Chemical Constituents of Essential Oil
Screening for Development Potential
o Match chemical constituents of essential oil
with possible market uses o Evaluate application potential of essential oil o Evaluate theoretical yields, cost of production o Evaluate time and cost of development
Value Determination (Use Criteria) Preliminary study due to volume of possibilities
The Screening Process
Regulatory Screening
(FDAs, REACH, SCCP, BPD, etc)
Generation of Possibilities
Elimination of Possibilities
Leads to a number of potential possibilities that can be further studied
Potential essential oil crop
idea
Bio-prospecting Screening Protocols o Anti inflammatory o Anti microbial o UV absorbing o Anti ageing actives o Flavour & fragrance
application o Aromatherapy o Anti cancer
Desktop study
Knowledge Required o Essential oil applications o International market
(Flavour & fragrance, cosmetics, personal care, agro-chemical, aromatherapy, etc.)
o International regulations
Need to collaborate with industry parties
Ethno-botany
Other literature (Journals,
etc.)
Study of same
latitude Crops
What has value to industry?
o Chemical
constituents o Odour/flavour
profile o Potential
applications
Match chemical constituents with possible market
uses
Evaluate application potential of essential oil
Evaluate theoretical yields, cost of production
Evaluate time and cost of
development
Value Determination (Preliminary study due to volume of possibilities)
Choice and Access to Market
Jurisdiction Regulatory Framework
Ylang Ylang (Cananga odorata)
benzyl acetate (ca. 25 %), p-cresyl methyl ether (ca. 20 %), methyl benzoate (ca. 5 %), methyl salicylate, cinnamyl acetate, (-)-linalool (ca. 15 %), geranyl acetate (ca. 10 %), farnesyl acetate (ca. 3 %), as well as a number of other sesquiterpenes and their oxygenated derivatives, e.g. muurolol T (ca. 2 %)
Extraction Method: Steam distillation of the flowers
Origin: Indonesia, Madagascar
Patchouli Oil (Pogostemon cablin)
(-)-patchoulol andnorpatchoulenol
Obtained by steam distillation under pressure or CO2-extraction of the dried leaves
Patchouli is mostly grown in Indonesia
There are no synthetic equivalents of the patchouli scent.
Main Constituents: (-)-patchoulol (30-40 %). However, it is maintained that norpatchoulenol, present in only 0.3-0.4 %, is playing a principal part in the overall odour picture.
Pandanus Oil (Pandanus odoratissimus)
phenethyl methyl etherpandanol
Origin: native of South East Asia and is much cultivated on the Indian East Coast
The flowers are hydro-distilled to yield a 'kewda attar
phenethyl methyl ether (pandanol) (38 %), together with terpinen-4-ol (19 %), alpha-terpineol (8 %) and phenethyl alcohol (7 %) [79]. Phenethyl alcohol and its derivatives are common odorants in flowers
Backhousia citriodora (Lemon Myrtle)
High Investment to Expand Industry in Australia
Strong Demand as an Ingredient for tea
Good Crop to Grow in Most Parts of Thailand
CHO
CHO
Citral (geranial 51.43 % and neral 42.12 % )
Important New Compounds Rose oil – What’s Important
Component % of OilThreshold in
ppbOdor Units
x 10-3
Rel. % of odor
units(-)-Citronellol 38 40 9500 4.3C14 - C16 Paraffins 16 - - -Geraniol 14 75 1860 0.8Nerol 7 300 233 0.1Phenethyl alcohol 2.8 750 37 0.016Eugenol methyl ether 2.4 820 29 0.013Eugenol 1.2 30 400 0.18Farnesol 1.2 20 600 0.27Linalool 1.4 6 2300 1(-)-Rose oxide 0.46 0.5 9200 4.1(-)-Carvone 0.41 50 82 0.036Rose furan 0.16 200 8 0.003beta-Damascenone 0.14 0.009 156000 70beta-Ionone 0.03 0.007 42860 19.2
Odor Unit = ConcentrationOdor Threshold
O
CH3
CH3CH3
CH3 CH3
CH3
CH3
O
CH3
CH3 CH3
OH
CH3 CH3
CH3
O
CH3
Physical Protection
Increase/decrease Plant architecture
Leaf shapes Colours
Special features (i.e., spikes, etc)
Secondary Metabolites
Repellents Attractants
Ingestion inhibitors Taste
Camouflage odours
Plant
Signals
Direct & indirect
Dual action
Increase/decr
ease production
Vary
production & dissipation
Direct & Indirect Responses
Herbivory (Predators)
Sign
al
Resp
onse
s
Insect Elicitors
Insects
Avoid “dangerous” metabolites
Produce counter metabolites (i.e.,
digestion enzymes)
Time/ spatial avoidance
Plant Repair
Heat Drought
UV Stress Flood & water
logging Lack of nutrients
Plant damage
Environment Changes
Oxygen
Carbon Dioxide
Water
Nitrates & Mineral Salts
Glycose
Polysaccharides & Disaccharides
Glycolysis
6-Deoxyxylulose
Isoprenoids (terpenoids)
Erythrose 4-phosphate
Pentose Phosphate Pathway
Phosphoenol pyruate
Pyruvate Hydroxy-
Benzoic Acid
Shikimate Pathway
Alkaloids
Phenylpropanoids
Complex Alkaloids
KREBS CYCLE
Acetyl-CoA
Malonyl-CoA
Mevalonic Acid
Complex Isoprenoids (terpenoids) Polyketides
Flavonoids
Complex Flavonoids
Primary Metabolites (in blue) Secondary Metabolites (in red)
Aromatic Amino Acids
Amino Acids & Nucleotides
Photosynthesis
Triglycerides
Shikimate
Chorismate
Prephenate
p-hydroxybenzoate
p-aminobenzoate
Phenylalanine
Cinnamic Acids
Tyrosine
Alkaloides
Aromatic Amino Acids
Anthranilate
Tryptophan
Phenyl-C3 Compounds
Phenyl-C1 Compounds
Flavonoids
The Shikimic Acid Pathway
Acetyl CoA
3-methylglutaryl CoA (HMG-CoA)
Mevalonate
Isoprenyldiphosphate (IPP) and Dimethyllallyldiphosphate (DMAPP)
Geranyl pyrophosphate (GPP)
Geranyl geranyl pyrophosphate
(GGPP)
Other Terpenes (Triterpenes & Tetraterpenes)
C30+ (6 Isoprene Units +)
Monoterpenes
Glyceraldehyde phosphate
Pyruvate
Mevalonate Pathway
Deoxyxylulose Phosphate Pathway
Farnesylpyrophosphate (FPP)
Sesquiterpenes
C5 (1 Isoprene Unit)
C10 (2 Isoprene Units)
C15 (3 Isoprene Units)
Diterpenes & Carotenoids
C20 (4 Isoprene Units)
Ionones (from degraded carotenoids)
Esters
Transacylase (coenzyme)
Dihydrofolate Reductase (coenzyme)
Dihydrofolate Reductase (coenzyme)
Aldehydes & Ketones
Alcohols Acids (carboxlic)
& Acyl CoA
Sulfate
ATP Sulphurlyase
Adenylation
Adenosin 5’-phosphosulphate
(APS)
Phosphorised
APS reductase
Sulfite
Sulfide O-acetylserine (thiol)lyase
Ferrodoxin-dependent sulphite
reductase
Cysteine
O-acetylserine
3’-phosphate 5-phosphosulphate
(PAPS)
APS Kinase
PAPS Reductase
Primary Sulphur Reduction Pathway
Minor Sulphur Reduction Pathway
0
5
10
15
20
25
30
35
40
Time of the Day
Perc
enta
ge o
f Tot
al V
olat
iles
1800 2400 0600 1200 1800 2400 0600 1200 1800 2400
Figure 9.5. Chemotype Variances within the Genotype Tanacetum vulgare L.
Tansy Tanacetum vulgare L
(Asteraceae)
Genotype Chemotypes
Camphor Type
1,8-Cineole Type
Artemisia ketone Type
Thujone Type
Myrtenol Type
Chemotype Variances
Other Chemotype
Compound C1 C2 C3 1,8-Cineole 16.0 27.2 14.5 Borneol 1.8 0.1 0.8 Camphor 16.2 9.8 0.5 Terpenin-4-ol 2.4 13.8 1.9 Myrtenol 24.9 10.6 15.8 E-Nerolidol Tr. 1.7 0.6 a-pinene 5.5 4.9 0.5 ß-pinene 2.2 2.3 Tr. Spathulenol 1.3 1.7 1.8 a-thujene Tr. 0.1 Tr. a-Terpinene 0.5 3.1 0.5 Ў-Terpinene 0.9 5.6 0.3 o-Cymene 0.7 3.4 0.3 Sabinene 1.7 1.7 Tr. Camphene 1.5 0.8 1.1
Sample Linalool Methyl chavical
Olfactory Profile
India 14.2% 77.5% A grassy herbaceous and mildly spicy predominating note, with an herbaceous subsidiary note; back notes slightly fruity.
French 55.3% 10.9% A smooth fresh and diffusive herbaceous note with harmonized cool anisic and slightly balsamic subsidiary notes and warm woody back notes.
Australian 34.3% 34.7% A clean vegetable type note with a cool herbaceous menthol-like subsidiary note; a green and grassy back note.
Seychelles 27.7% 40.2% A sharp diffusive clean grassy herbaceous note, with a fruity anisic subsidiary note and a very slightly camphoraceous back note.
(Australian grown)
3.4% 75.7% A sharp, if not somewhat dry, anisic note; the subsidiary notes were herbaceous with a slight sweet camphoraceous floral back note.
Different Major Chemical and Olfactory Profiles of Five Basil Oils
Influencing Factors Compound
characteristics (volatility/mol. Weight) Surrounding Material
Distillation
Historical
Solvent Extraction
Cold Pressing
Highly volatile terpenes
Compounds mixed with waxes, also lactones, esters etc. Low/medium volatility/stable
Influencing Factors Price vis. Market
Volume Plant cell structures
Field size Topography
Soil/field characteristics Part of plant (i.e.,
rhizome/leaf) Coppice
Automated harvest and distillation
system
Harvest and later load system
Manual harvesting
due to scale,
material, investment
Extensive large scale
farming High --- Low
Value
Specialties Distillation
Hydro
Water-Steam
Steam
Material Characteristics
Material Characteristics
Solubility in water
CO2 ‘Finer’
composition spectrum
Fractional Distillation
Individual aroma
compounds
Carbon dioxide Glycolysis Glucose 2 Acetyl CoA Fatty acid Acetoacetyl-CoA thiolase Acetocetyl CoA HMGS-CoA syntesis 3-hydroxy-3-methyl-glutaryl-CoA (HMG-CoA) HMGL-CoA lyase HMGR-CoA reductase Mevalonate Mevalonate pyrophosphate IPP isomerase Isopentenyl pyrophosphate (IPP) DMAPP (C5) Monoterpene synthases and cyclase Geranyl pyrophosphate (C10) prenyltransferase Farnesyl pyrophosphate (FPP) (C15) Sesquiterpene Synthesis & Cyclase Diterpene synthase & Cyclase Squalene syntase Geranyl geranylpyrophosphate (C20) Squalene (C30)
Cytokinins Isopentyl adenine
rubber
Monoterpeness
Sesquiterpenes Polyprenols
Farnesylated proteins
Sterols Saponins Hormones
Lipoproteins
Diterpenes Carotenoids Abscisic acid Chlorophyll Vitamin K
IPP DMPP Isomerization Geranyl-PP (+)-3S-Linayl-PP Monoterpene cyclase (-)-Boynyl-PP (-)-Camphene (+)-Isobornyl acetate (-)-Camphor Dehydrogenase (-)-Bornyl (-)-Camphor Dehydrogenase (+)-cis-sabinol (+)-Sabinone (+)-3-Thujone (a-thujone) (-)-3-Isothujone (ß-thujone)
beta-Pinene
Myrcene
Linalool
Geraniol Citronellol Citronellal
MentholLinalyl Acetate
1959 – Bain & Webb – Turpentine into Fragrance & Flavor
CH3CH3
C H2
C H 2
CH 3 C H3
C H2
CH 3
CH3 C H3
C H2
O H
CH 3
CH 3 CH 3
O H
C H3
CH3 C H3
O H
C H 3
CH 3 CH3
O
C H 3
CH 3 CH 3
O H
CH3
CH 3 CH 3
CH 2
O
OCH 3
Points to Remember
• The highest probability is not necessarily the correct one
• Check back to see if that chemical could physically be present
• You will have to add new materials to your database (Both NIST & Wiley databases)
• Is it an artifact? • Confirm your analysis with other supportive data
QC lab. in the days before the concept of ‘Health & Safety at Work’ – note lighted cigarettes dangling from lips of staff!
Gas Chromatography – Mass Spectrometry
GC-MS analysis Detective work
Looking at metabolite paths Olfactory analysis of living plants
Third Nobel Prize in this field
Helps elucidate many of the C10H16 group terpene structures present in essential oils utilizing common reagents such as hydrogen chloride and hydrogen bromide. In 1909 he published the results of his extensive studies in the book Terpene und Campher, a volume of 600 pages dedicated to his pupils.
CH3
CH3CH3
CH3
CH3CH2
CH2
CH3
CH3
CH3CH3
CH3O
beta-Pinenealpha-Pinene
CampheneCamphor
No. 3: Nobel Prize in Chemistry 1910 – Otto Wallach
In the perfumery and sesquiterpene domain - the total syntheses of nerolidol and farnesol.
From Jasmine - established the structure of jasmone. Elucidated the structures of the naturally occurring
musk perfumes, civetone and muscone thus replacing scents prized since antiquity – but only available from endangered species.
OO CH3
Civetone MusconeCivet CatViverra civetta
Musk DeerMoschus moschiferus L.
Nobel Prize in Chemistry 1939 - Leopold Ruzicka
Fourth Nobel Prize in this field