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GCMS presentation - natural products

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Using CGMS as a forensic tool in discovering natural materials and creating fragrances

Using CGMS as a forensic tool in discovering natural materials and creating fragrances

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  • 1. The Metabolite Map for Identifying Probabilities and Olfactory Analysis As A Supplement to GCMS Analysis
    Murray Hunter
  • 2. 1. Olfactory Evaluation
    2. Using CGMS in Forensic Fragrance Construction
    3. Using CGMS in Identifying Essential oil constituents
    4. Using CGMS in Quality Assurance of Flavours & fragrances
  • 3. What are essential oils?
  • 4. Essential Oil
    A 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 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.
  • 6. The Natural Aromatic Product Family
  • 7. Olfactory Evaluation
  • 8. ?
    The Olfactory System & Odour Classification
  • 9. The Human Olfactory System
    Odour molecules pass through the olfactory organ
  • 10. Olfactory epithelium
    Olfactory mucosa
    Mucus!
    High in nasal cavity
    Site of transduction
    Contains olfactory receptor neurons (ORN)
  • 11. 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
  • 12. Transmission
    Olfactory Receptors
    Olfactory 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 & reproduction
    Olfactory Disorder
    Anosmia: the general lack of olfaction
    Specific Anosmia: the inability to smell a specific chemical
  • 13. 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
  • 14. Olfactory Bulbs
    An outcropping of the brain
    Its like a snail in your brain!
    Electrical responses in cilia passed through olfactory nerve to OB
  • 15. 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
  • 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 Fragrance
    Top Notes
    Bergamot 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, Phenylacetaldehyde
    Middle Notes
    “ Heart of fragrance”.
    Intermediate Volale
    Floral, Aldehydic notes…..
    Vetiveryl acetate, Sandalwood, Isoeugenol, Vanillin 1.5%, Coumarin 15%, Nitromusks 10%
    Base Notes
    Basic of fragrance”.
    (Bottom) Low Volatile
    Woody, Powdery, Musky …..
  • 18. Classification of Odours
    Curtis & Williams (1994)
  • 19. Floral Family Descriptions
  • 20. Woody Family Descriptions
    Animalic Family Descriptions
  • 21. Balsamic Family Descriptions
    Herbaceous Family Descriptions
    Agrestic Family Descriptions
  • 22. Green Family Descriptions
    Minty Family Descriptions
    Coniferous Family Description
  • 23. Marine Family Descriptions
    Aldehydic Family Descriptions
    Medicated Family Descriptions
  • 24. Fruity Family Descriptions
    Sub-Class (Citrus)
  • 25. Spicy Family Description
    Miscellaneous Notes
  • 26. Odour Characteristics
    Additional Characteristics
  • 27. Fragrance Description Workshop
  • 28.
  • 29.
  • 30. Performance Test
    GC-MS
    A Fragrance Development Lab
    A trained human more accurate than a GC-MS
  • 31. Sample of a Flavour Chart
  • 32.
  • 33. Using CGMS in Forensic Fragrance Construction
    From This
    To This
  • 34.
  • 35.
  • 36. Apples aren't the same
    Sweet, sour, green, red, sharp, fresh, wholesome, etc.
    This means different aromatic chemicals play a role in fragrance
  • 37.
  • 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 – 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.
    (+)-Nootkatone
    strong grapefruit odor,
    bitter in taste
    (-)-Nootkatone
    weak woody (vetiver note);
    no grapefruit character;
    virtually no taste
    Threshold: 60,000 ppb 800 ppb
  • 42. 1970’s-80’s – Other Furanones
    Sotolon (caramel furanone) & Maple furanone identified in cane sugar – powerful caramel maple notes
    Maple Furanone (Abhexone)
    Sotolon
    Threshold: 0.003 ppb 0.00005 ppb
    Sotolon – key flavorant of fenugreek, sake, sherry wine
  • 43. 1968 – Pfizer patents Ethyl maltol
    Ethyl maltol (Veltol Plus®) was touted to be about 6X
    stronger than maltol and an important substitute for
    Coumarin. Well, at least it is stronger than maltol.
  • 44. 1975 - Introduction of α-Damascone and β-Damascone
    1982 – Introduction of Damascenone
    1970 – Discovery Damascenone & β-Damascone
  • 45. 1974 – Thiomenthones identified in Buchu oil
    Key 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 Passionfruit
    1984 – 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 ppb
  • 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 also
    requires stabilization as it tends to rapidly cyclize to the thio
    analog of dihydropinol.
  • 48. Coumarinic p-Menthane Lactones
    Dihydromintlactone (1995)
    Wine lactone (1996)
    Mintlactone (1983)
    GRAS No. -- 3764 4032
    Odor: Vinous, lactonic Minty, coumarinic, Coumarinic, hay,
    (coconut) tenacious lactonic, tonka
    Flavor: Lactonic, sweet, herbal Coumarinic, fatty, Coumarinic, herbal lactonic, coconut
    Threshold*: 0.0000016ppb 0.00012 ppb 0.000039 ppb
    *In air
    Ref: 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 epijasmonate
    Methyl Jasmonate – odorant, insect pheromone, plant growth regulator
  • 50. Advances in Flavoring Materials
    Chirality & Odor - Methyl Jasmonate & Methyl Dihydrojasmonate
    ConfigurationOdor DescriptionOdor Threshold (in PPB)
    Methyl jasmonates
    1R,2R-(-)- Weak odor >70*
    1S,2S-(+)- Odorless Odorless
    1S,2R-(-)-epi- Odorless Odorless
    1R,2S-(+)-epi- Strong odor; floral, true jasmin-like 3*
    Ref: T.E. Acree et. al., J.Agric.Food.Chem. 1985
    Methyl dihydrojasmonates
    1R,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-jasmone
    1R,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
  • 51.                             
    Advances in Flavoring Materials
    2001 – Takasago’s Professor RyojiNoyori wins
    the 2001 Nobel Prize for Chemistry
  • 52.
  • 53.
  • 54. Individual Aromatic Chemicals
    Probable Constituents of an essential oil
  • 55. GC-MS Analysis of a Meat Flavor
    • Abundance
    Peak Identified as FurfurylMercaptan
    Powerful Coffee Aroma
    1.6e+07
    1.4e+07
    Peaks are 2-Methyl-2,3-dihydrofuran-3-thiol isomers
    Powerful meat-like aroma
    1.2e+07
    1e+07
    8000000
    6000000
    4000000
    2000000
    0
    12.00
    14.00
    16.00
    18.00
    20.00
    22.00
    24.00
    26.00
    28.00
    30.00
    32.00
    34.00
    36.00
    Time-->
  • 56. Basic Fragrance Types
    Citrus
    Floral
    Aldehydic
    Spicy
  • 59.
    • Citrus notes
    Citrus + Floral
    • Representative Ingredients
    Natural : Lemon Oil, Bergamote, Lime….
    Chemical : Citral, Dihydo Myrcenol….
    Eau Savage
    Bergamot
    Lemon
    Orange
    • Representative Fine Fragrance
    O de Lancome (1975. Lancome)
    Bulgari Eau Parfume (1992. Bulgari)
    CK one (1994. C.Klein)
    Eau Savage (1966.C.Dior)
    Rose
    Jasmine
    Lily of Valley
    Oakmoss
    Ambergris
    Civet
  • 60.
    • Citrus notes
    CK One
    Bergamot
    Lemon
    Mandarin
    Dihydro Myrcenol
    Citrus
    Green
    Floral
    Jasmin
    Muguet
    Amber
    Musk
    Sandalwood
    Amber
    Woody Musk
  • 61.
    • Floral notes
    Floral + Floral
    JOY
    • Representative Ingredients
    Natural : Jamine Abs, Ylang Ylang, Rose Abs.
    Tuberose ….
    Chemical : Hedion, Benzyl Acetate….
    Green
    Green
    • Representative Fine Fragrance
    Joy (1935. Jean Patou)
    Diorssimo (1956.C.Dior)
    Anais Anais (1979. Cacharel)
    Paris (1983. YSL)
    Beautiful (1985. E. Lauder)
    Jasmine
    Rose
    Ylang Ylang
    Violet
    Muguet
    Floral
    Musk
    Sandalwood
    Powdery
    Musk
    Woody
    Powdery
  • 62. Chanel No. 5
    Aldehyd 10
    Muguet
    Ylang-Ylang
    Floral
    Jasmine
    Rose
    Carnation
    Aldehyde C-11
    Aldehyde C-12
    Aldehyddic
    Woody
    Powder
    Vanilla
    Sandalwood
    Musk
    • Aldehydic notes
    Floral + Aldehydic
    • Representative Ingredients
    Natural : 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)
  • 63. L'Air du temps
    Bergamot
    Ylang Ylang
    Floral
    Carnation
    Jasmine
    Rose
    Iris
    Spicy Floral
    Sandalwood
    Cedarwood
    Musk
    Woody
    Musk
    • Spicy notes
    Floral + Spicy
    • Representative Ingredients
    Natural : 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)
  • 64.
    • Representative Ingredients
    Natural : Oak moss Abs. Vertiver, Patchouli oil
    Galbanum Cederwood, Sandalwood
    Chemical : Veramoss, Iso E Super..….
    Citrus
    Green
    Aldehyde
    • Representative Fine Fragrance
    Mitsouko (1919. Guerlain)
    Miss Dior (1947. Christian Dior)
    Coco (1984. Chanel)
    Ysatis (1984. Givenchy)
    Floral (Jasmine,
    Rose, Ylang…)
    Woody
    Mossy
    Patchouli
    What is Chypre….?
    • Chypre notes
    • Chypre notes - Fine Fragrance
    Bergamot
    Mandarin
    Galbanum
    AldehydC-11
    Citrus
    Green
    Aldehyde
    COCO
    Jasmine
    Rose
    Ylang-Ylang
    Muguet
    Oriental
    Floral
    Amber
    Woody
    Mossy
    Amber
    Mossy
    Patchouli
    Mossy
    Woody
  • 65. Citrus
    Mandarin
    Lemon
    Spicy(cinamon..)
    Floral
    Vanilla Abs.
    Sweet
    Balsam
    What is Oriental….?
    • Oriental notes
    • 66. Representative Ingredients
    Natural : 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)
  • 67.
    • Fougere notes - Fine Fragrance
    Bergamot
    Lavendin
    Clove
    Spearmint
    Herbacious
    Drakkar Noir
    Muguet
    Geranium
    Carnation
    Floral
    Woody
    Powdery
    Powdery
    Mossy
    Cederwood
  • 68.
  • 69. Using CGMS in Identifying
    Essential oil constituents
  • 70.
  • 71.
  • 72.
  • 73.
  • 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 flowers
    Origin: 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 andnorpatchoulenol
    Obtained by steam
    distillation under
    pressure or CO2-
    extraction of the
    dried leaves
    Patchouli is mostly
    grown in Indonesia
  • 76. Pandanus Oil (Pandanus odoratissimus)
    phenethyl methyl etherpandanol
    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
    The flowers are hydro-distilled to yield a 'kewda attar
    Origin: 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 Australia
    Strong Demand as an Ingredient for tea
    Good Crop to Grow in Most Parts of Thailand
    Citral (geranial 51.43 %
    and neral 42.12 % )
  • 78. Important New Compounds
    • Rose oil – What’s Important
    Concentration
    Odor Unit =
    Odor Threshold
  • 79.
  • 80.
  • 81.
  • 82.
  • 83.
  • 84.
  • 85.
  • 86.
  • 87.
  • 88. Different Major Chemical and Olfactory Profiles of Five Basil Oils
  • 89.
  • 90.
  • 91.
  • 92.
  • 93. Harvest Timing Critical for Some Crops (Mentha piperata)
  • 94. 1959 – Bain & Webb – Turpentine into Fragrance & Flavor
    beta-Pinene
    Linalool
    Linalyl Acetate
    Menthol
    Myrcene
    Geraniol
    Citronellol
    Citronellal
  • 95. 1959 – Roche Process for Linalool & Citral via Acetylene
  • 96. 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
  • 97.
  • 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!
  • 100.
  • 101. Gas Chromatography – Mass Spectrometry
    Detective work
    GC-MS analysis
    Looking at metabolite paths
    Olfactory analysis of living plants
  • 102. Third Nobel Prize in this field
    • No. 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-Pinene
    alpha-Pinene
    Camphene
    Camphor
  • 104. Fourth Nobel Prize in this field
    • Nobel 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.
    Civetone
    Muscone
    Musk Deer
    Moschusmoschiferus L.
    Civet Cat
    Viverracivetta
  • 107. Have fun with your new toy
    Thank You

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