GCMS presentation - natural products
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This document discusses the use of gas chromatography-mass spectrometry (GC-MS) analysis and human olfactory evaluation in forensic fragrance construction and quality assurance of flavors and fragrances. It provides background on essential oils, concretes, and absolutes. It also covers the human olfactory system, odor classification, fragrance structure, and advances in flavor materials discovered through GC-MS analysis. Key compounds discussed include damascenones, furanones, and methyl jasmonate. Common fragrance types like citrus, floral, aldehydic, oriental, chypre, and fougere are also outlined.
![Pandanus Oil (Pandanus odoratissimus)phenethyl methyl etherpandanolphenethyl 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 flowersThe flowers are hydro-distilled to yield a 'kewda attarOrigin: native of South East Asia and is much cultivated on the Indian East Coast](https://image.slidesharecdn.com/cgmspresentation-110814100314-phpapp01/85/GCMS-presentation-natural-products-76-320.jpg)
GCMS presentation - natural products
- 1. The Metabolite Map for Identifying Probabilities and Olfactory Analysis As A Supplement to GCMS Analysis Murray Hunter
- 2. 1. Olfactory Evaluation2. Using CGMS in Forensic Fragrance Construction3. Using CGMS in Identifying Essential oil constituents4. Using CGMS in Quality Assurance of Flavours & fragrances
- 3. What are essential oils?
- 4. 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
- 5. Concretes and AbsolutesVolatiles 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.
- 6. The Natural Aromatic Product Family
- 8. ?The Olfactory System & Odour Classification
- 9. The Human Olfactory SystemOdour molecules pass through the olfactory organ
- 10. Olfactory epitheliumOlfactory mucosaMucus!High in nasal cavitySite of transductionContains olfactory receptor neurons (ORN)
- 11. 11Nose hair: Olfactory ciliaORN have ciliaCilia contain olfactory receptor proteinsSimilar to visual pigmentTransductionOdorants bind to ORsChange shape of proteinIon flow across ORElectricity
- 12. TransmissionOlfactory ReceptorsOlfactory Cells line the Olfactory Epithelium which is responsible for olfaction Each cell has cilia where receptor sites are located Replaced every month Axons of the olfactory receptors carry information to the olfactory bulb Olfactory 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 & reproductionOlfactory DisorderAnosmia: the general lack of olfaction Specific Anosmia: the inability to smell a specific chemical
- 13. 13How many receptor types are there?1000 different kinds of olfactory receptors (OR)10 million OR neurons10,000 of each type of OREach OR neuron has only one type of receptor1000 neuronal chemical detectorsPotential to differentiate between 5,000-10,000 different odours
- 14. Olfactory BulbsAn outcropping of the brainIts like a snail in your brain!Electrical responses in cilia passed through olfactory nerve to OB
- 15. The hedonic primacy of olfactionSensory and emotional experienceNot the same for vision/auditionSeeing and feeling more distinctMore intertwined in the chemical sensesWhy?Orbitofrontal cortexPlays multiple rolesCritical for emotional experienceSecondary sensory cortex for olfactionAlso centre of creativity and imagination
- 16. The olfactory interpretation process from input to response
- 17. 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.The Structure of a FragranceTop NotesBergamot oil, Rosewood oil (linalool), Linalyl acetate, Neroli oil, Ciste Oil“First Impression” in Perfume. High Volatile Citrus, Fresh, Green notes…..Rose Oil 5%, Jasmin absolute 4%, Ylang Ylang Oil, Aldehyde C11, C12, Methyl ionone 8%, hydroxycitronellal 10%, Cinamic Alcohol, Styrax. Phenol ethyl alcohol, PhenylacetaldehydeMiddle Notes“ Heart of fragrance”. Intermediate VolaleFloral, Aldehydic notes…..Vetiveryl acetate, Sandalwood, Isoeugenol, Vanillin 1.5%, Coumarin 15%, Nitromusks 10% Base NotesBasic of fragrance”.(Bottom) Low VolatileWoody, Powdery, Musky …..
- 18. Classification of OdoursCurtis & Williams (1994)
- 20. Woody Family DescriptionsAnimalic Family Descriptions
- 21. Balsamic Family DescriptionsHerbaceous Family DescriptionsAgrestic Family Descriptions
- 22. Green Family DescriptionsMinty Family DescriptionsConiferous Family Description
- 23. Marine Family DescriptionsAldehydic Family DescriptionsMedicated Family Descriptions
- 24. Fruity Family DescriptionsSub-Class (Citrus)
- 25. Spicy Family DescriptionMiscellaneous Notes
- 30. Performance TestGC-MSA Fragrance Development LabA trained human more accurate than a GC-MS
- 31. Sample of a Flavour Chart
- 33. Using CGMS in Forensic Fragrance ConstructionFrom ThisTo This
- 36. Apples aren't the sameSweet, sour, green, red, sharp, fresh, wholesome, etc.This means different aromatic chemicals play a role in fragrance
- 38. Discovered in 1937, the First Publication on Raspberry Ketone appears in 1961
- 39. 1964 – Introduction of Furaneol®1965 – First publications on isolation of Furaneol®from strawberry and pineapple
- 40. 1965-66 – α- & β-Sinensal isolated from orange oil
- 41. 1960’s – NootkatoneFirst 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.(+)-Nootkatonestrong grapefruit odor, bitter in taste (-)-Nootkatoneweak woody (vetiver note); no grapefruit character; virtually no tasteThreshold: 60,000 ppb 800 ppb
- 42. 1970’s-80’s – Other FuranonesSotolon (caramel furanone) & Maple furanone identified in cane sugar – powerful caramel maple notesMaple Furanone (Abhexone)SotolonThreshold: 0.003 ppb 0.00005 ppbSotolon – key flavorant of fenugreek, sake, sherry wine
- 43. 1968 – Pfizer patents Ethyl maltolEthyl 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.
- 44. 1975 - Introduction of α-Damascone and β-Damascone1982 – Introduction of Damascenone1970 – Discovery Damascenone & β-Damascone
- 45. 1974 – Thiomenthones identified in Buchu oilKey component for black currant and the “fuzzy” peach skin note
- 46. 1980 – Patent on Oxane®1977 - Winter identifies 2-methyl-4-propyl-1,3-oxathiane as a character impact compound in Passionfruit1984 – Pickenhagen determines that (-)- cis- 2-methyl-4-propyl-1,3-oxathiane is the important diastereomer(-)-(2R,4S)-2-methyl-4-propyl-1,3-oxathiane Odor: powerful sulfury, tropical fruit
- 47. Threshold: 2 ppb(+)-(2S,4R)-2-methyl-4-propyl-1,3-oxathiane Odor: flat, estery, camphoraceous, floral, less sulfury Threshold:4 ppb1982 – 1-p-Menthene-8-thiolDemole 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 thioanalog of dihydropinol.
- 48. Coumarinic p-Menthane LactonesDihydromintlactone (1995)Wine lactone (1996)Mintlactone (1983)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., FlavourFragr. J., 2002; 17: 218–226;Gaudin, Tetrahedron, 2000, 56: 4769-4776
- 49. 1962 – First publications appear on Methyl Jasmonate & Methyl Dihydrojasmonate 1R,2R-(-)-Z-methyl jasmonate 1S,2S-(+)-Z-methyl jasmonate 1R,2S-(+)-Z-methyl epijasmonate 1S,2R-(-)-Z-methyl epijasmonateMethyl Jasmonate – odorant, insect pheromone, plant growth regulator
- 50. Advances in Flavoring MaterialsChirality & Odor - Methyl Jasmonate & Methyl DihydrojasmonateConfigurationOdor DescriptionOdor 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 lastingRef: Werkhoff, P., et. al., Food Reviews International, 2002* detection threshold**recognition threshold
- 51. Advances in Flavoring Materials2001 – Takasago’s Professor RyojiNoyori wins the 2001 Nobel Prize for Chemistry
- 54. Individual Aromatic ChemicalsProbable Constituents of an essential oil
- 55. GC-MS Analysis of a Meat FlavorAbundancePeak Identified as FurfurylMercaptanPowerful Coffee Aroma 1.6e+07 1.4e+07Peaks are 2-Methyl-2,3-dihydrofuran-3-thiol isomersPowerful meat-like aroma 1.2e+07 1e+078000000600000040000002000000012.0014.0016.0018.0020.0022.0024.0026.0028.0030.0032.0034.0036.00Time-->
- 57. Chypre
- 59. Citrus notes Citrus + FloralRepresentative IngredientsNatural : Lemon Oil, Bergamote, Lime….Chemical : Citral, Dihydo Myrcenol…. Eau SavageBergamotLemonOrange Representative Fine FragranceO de Lancome (1975. Lancome)Bulgari Eau Parfume (1992. Bulgari)CK one (1994. C.Klein) Eau Savage (1966.C.Dior)Rose JasmineLily of ValleyOakmossAmbergrisCivet
- 60. Citrus notes CK OneBergamotLemonMandarinDihydro Myrcenol CitrusGreenFloralJasminMuguetAmberMuskSandalwoodAmberWoody Musk
- 61. Floral notes Floral + FloralJOYRepresentative IngredientsNatural : Jamine Abs, Ylang Ylang, Rose Abs. Tuberose ….Chemical : Hedion, Benzyl Acetate….Green Green Representative Fine FragranceJoy (1935. Jean Patou)Diorssimo (1956.C.Dior)Anais Anais (1979. Cacharel)Paris (1983. YSL)Beautiful (1985. E. Lauder)JasmineRose Ylang YlangVioletMuguetFloral MuskSandalwoodPowderyMuskWoodyPowdery
- 62. Chanel No. 5Aldehyd 10MuguetYlang-Ylang FloralJasmineRoseCarnationAldehyde C-11Aldehyde C-12AldehyddicWoodyPowderVanillaSandalwoodMuskAldehydic notes Floral + AldehydicRepresentative IngredientsNatural : Not available Chemical : Aldehyde C-11, Aldehyde C-12..….Representative Fine FragranceChanel No. 5 (1921. Chanel)Calandre (1969. 1969. Rabanne)First (1976. Van Cleef & Arpels)
- 63. L'Air du tempsBergamotYlang Ylang FloralCarnationJasmineRoseIrisSpicy FloralSandalwoodCedarwoodMuskWoodyMuskSpicy notes Floral + SpicyRepresentative IngredientsNatural : Clove Buds oil, Pepper oil, Cinnamon oil. Carnation……. Chemical : Eugenol, Cinnamic Aldehyde ..….Representative Fine FragranceL’air du Temps (1948. Nina Ricci)Fidji (1966. Guy Laroche)Egoist (1990. Chanel)
- 64. Representative IngredientsNatural : Oak moss Abs. Vertiver, Patchouli oil Galbanum Cederwood, SandalwoodChemical : Veramoss, Iso E Super..….Citrus Green AldehydeRepresentative Fine FragranceMitsouko (1919. Guerlain)Miss Dior (1947. Christian Dior)Coco (1984. Chanel)Ysatis (1984. Givenchy)Floral (Jasmine, Rose, Ylang…)WoodyMossyPatchouliWhat is Chypre….?Chypre notes Chypre notes - Fine Fragrance BergamotMandarinGalbanumAldehydC-11CitrusGreenAldehydeCOCOJasmineRose Ylang-YlangMuguetOrientalFloralAmberWoodyMossyAmberMossyPatchouliMossyWoody
- 65. Citrus MandarinLemonSpicy(cinamon..)FloralVanilla Abs.SweetBalsamWhat is Oriental….?Oriental notes
- 66. Representative IngredientsNatural : Vanilla, Tolu Balsam, Mandarin, Cinnamon Chemical : Vanillin, Galaxolide..….Representative Fine FragranceShalimar (1925. Guelain)Obsession (1984. Calvin Klein)Opium (1977. YSL)Samsara (1989. Guelain)Jean Paul Gaultier (1993. J.P.Gaultier)
- 67. Fougere notes - Fine FragranceBergamotLavendinCloveSpearmintHerbaciousDrakkar NoirMuguetGeraniumCarnationFloralWoodyPowderyPowderyMossyCederwood
- 69. Using CGMS in Identifying Essential oil constituents
- 74. 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 flowersOrigin: Indonesia, Madagascar
- 75. Patchouli Oil (Pogostemon cablin)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.(-)-patchoulol andnorpatchoulenolObtained by steam distillation under pressure or CO2-extraction of the dried leavesPatchouli is mostly grown in Indonesia
- 76. Pandanus Oil (Pandanus odoratissimus)phenethyl methyl etherpandanolphenethyl 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 flowersThe flowers are hydro-distilled to yield a 'kewda attarOrigin: native of South East Asia and is much cultivated on the Indian East Coast
- 77. Backhousia citriodora (Lemon Myrtle)High Investment to Expand Industry in AustraliaStrong Demand as an Ingredient for teaGood Crop to Grow in Most Parts of ThailandCitral (geranial 51.43 %and neral 42.12 % )
- 78. Important New CompoundsRose oil – What’s ImportantConcentrationOdor Unit =Odor Threshold
- 88. Different Major Chemical and Olfactory Profiles of Five Basil Oils
- 93. Harvest Timing Critical for Some Crops (Mentha piperata)
- 94. 1959 – Bain & Webb – Turpentine into Fragrance & Flavorbeta-PineneLinaloolLinalyl AcetateMentholMyrceneGeraniolCitronellolCitronellal
- 95. 1959 – Roche Process for Linalool & Citral via Acetylene
- 96. Points to RememberThe highest probability is not necessarily the correct oneCheck back to see if that chemical could physically be presentYou will have to add new materials to your database (Both NIST & Wiley databases)Is it an artifact? Confirm your analysis with other supportive data
- 98. Using CGMS in Quality Assurance of Flavours & fragrances
- 99. QC lab. in the days before the concept of ‘Health & Safety at Work’ – note lighted cigarettes dangling from lips of staff!
- 101. Gas Chromatography – Mass SpectrometryDetective workGC-MS analysisLooking at metabolite pathsOlfactory analysis of living plants
- 102. Third Nobel Prize in this fieldNo. 3: Nobel Prize in Chemistry 1910 – Otto Wallach
- 103. 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.beta-Pinenealpha-PineneCampheneCamphor
- 104. Fourth Nobel Prize in this fieldNobel Prize in Chemistry 1939 - Leopold Ruzicka
- 105. In the perfumery and sesquiterpene domain - the total syntheses of nerolidol and farnesol. From Jasmine - established the structure of jasmone.
- 106. Elucidated the structures of the naturally occurring musk perfumes, civetone and muscone thus replacing scents prized since antiquity – but only available from endangered species.CivetoneMusconeMusk DeerMoschusmoschiferus L.Civet CatViverracivetta
- 107. Have fun with your new toyThank You