Slide 1: The Art & Science of Fragrance & Flavor Creation John C. Leffingwell Society of Flavor Chemist’s December 4, 2003
Slide 2: Fragrance & Flavor – Art & Science  Conventional Market View – U.S. $15 Billion Worldwide Market Flavors vs. Fragrances Flavors 49% Fragrances 51%
Slide 3: Fragrance & Flavor – Art & Science  Conventional Market View – U.S. $15 Billion Western Europe Eastern Europe 5% M iddle East & Africa 6% 25% North America 32% Asia-Pacific 26% South America 6%
Slide 4: Fragrance & Flavor – Art & Science  Conventional Market View – U.S. $15 Billion Flavor & Fragance Market excluding Branded Soft Drink Concentrates Danisco - 1.7% (DK) 12% - International Flavors & Fragrances (US) Others - 35.4% 12.8% - Givaudan (CH) 7.6% - Quest Int'l (NL) Sensient - 2.8% (US) T. Hasegaaw a - 2.5 % (JP) Mane - 1.8% (FR) 9.1% - Firm enich (CH) 8.6% - Symrise (DE) Takasago - 5.6% (JP)
Slide 5: Fragrance & Flavor – Art & Science  The Real Market – U.S. $30 Billion Flavor & Fragrance Market Including Branded Soft Drink Concentrates Other Branded Soft Drinks Cadbury Schweppes 3% 3% 16% 39% Pepsico Flavor & Fragrance Coca-Cola 39%
Slide 6: Fragrance & Flavor – Art & Science  Fragrance & Flavor - The shaping of history  Prehistory - Culinary & Fragrant Oils Earliest items of commerce were most likely spices, gums and other fragrant plants.  Circa 7000 BC – Fragrant plants and spices infused in the fatty oils of Olive & Sesame for use as ointments
Slide 7: Fragrance & Flavor – Art & Science  The shaping of history  3000 BC – Indus Valley (Pakistan) - terra-cotta perfume containers and a primitive still - place it 3,000 years earlier than most sources date the invention of distillation. BC – Egyptians– when learning to write and make bricks, were already importing large quantities of myrrh.  3000
Slide 8: Fragrance & Flavor – Art & Science  The shaping of history - Egypt Perfume Vessel Symbolizing Unification - Reign of Tutankhamon Calcite pots filled with spices such as frankincense preserved in fat still gave off a faint odor when opened in King Tutankhamen's tomb after 3,000 years
Slide 9: Fragrance & Flavor – Art & Science  The shaping of history – Greece Greek Perfume Urns By the 7th century BC, Athens had developed into a mercantile center in which hundreds of perfumers set up shop. Trade was heavy in fragrant herbs such as marjoram, lily, thyme, sage, anise, rose and iris, infused into olive, almond, castor and linseed oils to make thick unguents. These were sold in small, elaborately decorated ceramic pots, similar to the small jars still sold in Athens today.
Slide 10: Fragrance & Flavor – Art & Science  The shaping of history – Greece circa 400 BC Still of Democritus Leucippus and Democritus – Fathers of the Atomic Theory The first firm documentary evidence of the distillation of essential oils is Herodotus' record of the method of distilling turpentine from 425 B.C.
Slide 11: Fragrance & Flavor – Art & Science  The shaping of history – Perfume basics - 300 BC  Socrates’ classmate, Theophrastus, sent plant cuttings obtained during his extensive travels, thus establishing a botanical garden in Athens. treatise “On Odors” covered all the basics: blending perfumes, shelf life, using wine with aromatics, substances that carry scent, and the effect of odor on the mind and body.  Theophrastus'
Slide 12: Fragrance & Flavor – Art & Science  The shaping of history – International Trade  As trade routes expanded, Africa, South Arabia and India began to supply spikenard and ginger to Middle Eastern and Mediterranean civilization. Phoenician merchants traded in Chinese camphor and Indian cinnamon, pepper and sandalwood.  True myrrh and frankincense from Yemen reached the Mediterranean by 300 BC, by way of Persian traders.  Demand increased for roses, sweet flag, orris root, narcissus, saffron, mastic, oak moss, cinnamon, cardamom, pepper, nutmeg, ginger, costus, spikenard, aloewood, grasses and gum resins.
Slide 13: Fragrance & Flavor – Art & Science  The shaping of history – Rome By the 1st century AD, Rome was using about 2,800 tons of imported frankincense and 550 tons of myrrh per year. Nero, Roman emperor in 54 AD, spent the equivalent of $100,000 to scent just one party he was giving. No “Orgy” was complete without perfume.
Slide 14: Fragrance & Flavor – Art & Science  The Modern Toga Party Former Tyco CEO Dennis Kozlowski Today’s Nero
Slide 15: Fragrance & Flavor – Art & Science  The shaping of history – Biblical Times Fragrance occurs, at least symbolically, throughout the New Testament. The frankincense and myrrh brought to the Christ child were more valuable than the gift of gold (if indeed it was gold; some speculate that the three wise men may have been carrying goldcolored, fragrant ambergris). "Then took Mary a pound of ointment of spikenard, very costly, and anointed the feet of Jesus, and wiped his feet with her hair: and the house was filled with the odour of the ointment." John 12:3
Slide 16: Fragrance & Flavor – Art & Science  The shaping of history – 1ST Century AD Mary Prophetissa (Prophetissima) aka Maria the Jewess The tribokos Invented the double boiler, also known as a Bain Marie, or Mary's Bath… as well as the first true still which she called the tribokos. It consisted of copper tubing, ceramic pottery, and metal. When heated, vapors from plant material and water would condense on the inside of the still, then trickle down and collect in a bottle.
Slide 17: Fragrance & Flavor – Art & Science  The shaping of history – 1ST Century AD Mary Prophetissa (Prophetissima) aka Maria the Jewess Her design and many later modifications were used to distill essential oils, but also proved useful for alcoholic beverages. And with the still dawned the new Age of Alchemy
Slide 18: Fragrance & Flavor – Art & Science  The shaping of history – 10 -11th Century AD Ibn Sina (Avicenna) – a famous Arab physician and alchemist that wrote over 400 books on medicine, philosophy, geology, mathematics, astronomy, and logic, is credited with significantly improving the art of distillation by adding a water cooled jacket around the cooling coil.
Slide 19: Fragrance & Flavor – Art & Science  The shaping of history – 10-14th Century AD The Arabs used their new technique to distill ethyl alcohol (ethanol) from fermented sugar, providing a new solvent for the extraction of plant oils in place of the fatty oils that had been used for millennia. Knowledge of distillation gradually spread around Europe through trading and crusading until essential oils had become a specialty of mediaeval pharmacies. Essential oils were so-named because they were thought to represent the very essence of odor, flavor & life. Their extraction was researched by alchemists in their search for the philosophers' stone that would turn common metals into gold.
Slide 20: Fragrance & Flavor – Art & Science  The shaping of history – Marco Polo 1271 - Marco Polo, at the age of seventeen years, embarked from Venice with his father and uncle on a trip that would last 24 years – and bring knowledge of the Orient and trade routes. Marco Polo lived for 16 years in China where he was employed for several years by Kublai Khan. He left China in 1292, returning to Venice (1295), and fought against the Genoese, but was captured. In prison he wrote of his adventures in 'Travels of Marco Polo' - a book which instantly fired the imagination of all Medieval Europe – and spurred a competition among nations that would last 500 years.
Slide 21: Fragrance & Flavor – Art & Science  The shaping of history – Marco Polo
Slide 22: Fragrance & Flavor – Art & Science  The shaping of history – Influence of Spice Trade In the 13th and 14th centuries, Italy monopolized the European Spice & Perfume material trade that had begun during the Crusades. One purpose of Marco Polo's journey to China was to bypass Moslem middlemen and their 300 percent markup in price by convincing the Orient to trade directly with Venice.
Slide 23: Fragrance & Flavor – Art & Science  The shaping of history – The Age of Exploration  1492 - Columbus discovered the Americas while looking for the spice islands of the Orient. Although, at the time, this failure was a great disappointment – there were many treasures that resulted. Vast quantities of gold, silver as well as new culinary items such as chocolate (cocoa). New fragrant treasures such as Vanilla, balsam of Peru and Tolu, juniper, American cedar and sassafras soon became available to Europeans.
Slide 24: Fragrance & Flavor – Art & Science  The shaping of history – Influence of Spice Trade 1497 1498 - Vasco da Gama departs Lisbon Portugal to discover the sea passage to the distant spice Indies. - Vasco da Gama arrives in India by rounding Africa via the Cape of Good Hope and Portugal becomes the ruler of the Indian ocean for nearly 150 years.
Slide 25: Fragrance & Flavor – Art & Science  The shaping of history – The Age of Colonization  1602 - Dutch East India Company granted a monopoly on the trade in the East Indies.  Purpose - trading spices like nutmeg, cloves, cinnamon and pepper, tea, silk and porcelain And – to prevent other European nations from entering the East Indies for trade.  Dec. 31, 1600 - Queen Elizabeth I grants a Royal Charter to the East India Company, but the Dutch massacre of the English at Amboyna in 1623 reduced them initially to picking up scraps of trade, either by piracy or dealing with intermediaries.
Slide 26: Fragrance & Flavor – Art & Science  The shaping of history – The Age of Colonization  By the mid 1600’s – the Dutch had driven the British and Portuguese from Indonesia, Malaya, and Ceylon (Sri Lanka), and controlled the fabulous trade of the Spice Islands.  1621 - the Dutch started a West India Company, which established the American province of New Netherland in 1624, and reputedly purchased what is now New York from the Native Americans for the equivalent of $24.  1664 - the English capture New Netherland  1673 - New York was recaptured by a Dutch fleet  1674 – The English negotiate peace and trade a small island off Indonesia (Rhun) for New York.
Slide 27: Fragrance & Flavor – Art & Science  The shaping of history – Spice Wars New York traded for Rhun – the best Nutmeg island
Slide 28: Fragrance & Flavor – Art & Science Quite A Trade
Slide 29: Fragrance & Flavor – Art & Science  The New Perfumers  Perfumed leather gloves became popular in France and in 1656, the guild of glove and perfume-makers was established in Grasse. The use of perfume in France grew steadily. The court of Louis XV was even named “the perfumed court”. In 1732, when the Italian Giovanni Maria Farina took over his uncle's business in Cologne, he produced aqua admirabilis, a lively blend of neroli, bergamot, lavender and rosemary in rectified grape spirit. This was splashed on the skin, and also used for treating sore gums and indigestion. French soldiers later stationed there dubbed it “eau de Cologne”.
Slide 30: Fragrance & Flavor – Art & Science  The shaping of history – France & Perfume 16th & 17th centuries - Southern France (Grasse) becomes a center of expertise for the growing, extraction and distillation of essential oils. France becomes the the Perfume center of the world. Large scale cultivation & processing of valuable plants for oils such as rose soon was centered there. And raw materials from around the world were imported for processing. Extraction & distillation techniques were refined.
Slide 31: Fragrance & Flavor – Art & Science  The shaping of history – France & Perfume
Slide 32: Fragrance & Flavor – Art & Science  Grasse France – The Center of Perfumery Perfume Factory - Grasse Lavender field near Grasse
Slide 33: Fragrance & Flavor – Art & Science  The Perfumers – Enfleurage process Flowers such as Jasmine are laid out on trays of fat that absorb the fragrance. The fat is later extracted with alcohol,and then concentrated into an absolute. Jasmine flowers laid out on the fat Preparing the frame with fat Grasse - Chiris factory - early 20th century
Slide 34: Fragrance & Flavor – Art & Science  The Production of Rose Oil
Slide 35: Fragrance & Flavor – Art & Science  The Production of Rose Oil
Slide 36: Fragrance & Flavor – Art & Science  The new partner – The Organic Chemist Mid-1800’s - From Germany came a new breed of Chemist that would revolutionize industry and bring an end to “Alchemy”. This type chemist used the scientific method to unravel chemical structures and create materials from coal, petroleum and other materials. 1855 – First synthesis of cinnamaldehyde 1868 – Commercial production of coumarin – the first synthetic fragrance chemical 1874 – Chemical structure of vanillin determined. 1876 – Synthetic vanillin production starts. 1850 to 1900 – Significant advances in elucidating major chemicals in Essential oils.
Slide 37: Fragrance & Flavor – Art & Science  The new partner – The Organic Chemist Nobel Prize in Chemistry 1910 – Otto Wallach 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 H3C CH3 CH3 H3C CH2 alpha-Pinene H3C CH3 beta-Pinene CH2 CH3 H3C Camphor O CH3 Camphene
Slide 38: Fragrance & Flavor – Art & Science  The new partner – The Organic Chemist Nobel Prize in Chemistry 1939 - Leopold Ruzicka 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. O O CH3 Civet Cat Viverra civetta Civetone Muscone Musk Deer Moschus moschiferus L.
Slide 39: Fragrance & Flavor – Art & Science  The new partner – The Organic Chemist Nobel Prize in Chemistry 2001 - Ryoji Noyori For chirally catalyzed hydrogenation reactions. In perfumery and flavors - the chiral (asymmetric) synthesis of Menthol & many other fragrance & flavor compounds. In the chiral synthesis of pharmaceutical & photochromic materials. CH3 CH3 OH H3C CH3 HO H3C CH3
Slide 40: Fragrance & Flavor – Art & Science  The new partner – The Organic Chemist 1950’s – Bain & Webb – Turpentine into Fragrance & Flavor H3C CH3 O O CH3 CH2 H3C OH H3C H3C CH2 beta-Pinene H3C CH2 CH3 H3C CH2 H3C OH CH3 CH3 Linalool Linalyl Acetate Menthol CH2 CH3 CH3 CH3 H3C CH3 OH H3C CH3 H3C OH CH3 H3C O CH3 Myrcene Geraniol Citronellol Citronellal
Slide 41: Fragrance & Flavor – Art & Science  Gas Chromatography – Mass Spectrometry GC-MS analysis Detective work Distillation & extraction Volatiles from a living flower
Slide 42: Fragrance & Flavor – Art & Science  Gas Chromatography – Mass Spectrometry GC-MS Analysis of a Meat Flavor Abundance 1.6e+07 1.4e+07 1.2e+07 1e+07 8000000 6000000 4000000 2000000 0 Time--> Peak Identified as Furfuryl Mercaptan Powerful Coffee Aroma SH O Peaks are 2-Methyl-2,3-dihydrofuran-3-thiol isomers Powerful meat-like aroma SH SH O CH3 O CH3 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
Slide 43: Fragrance & Flavor – Art & Science  Gas Chromatography – Mass Spectrometry Volatile Chemicals Identified in Foodstuffs 8000 7000 6000 Thousands 5000 4000 3000 2000 1000 0 1974 1979 1999 1963 1969 1984 1989 1994
Slide 44: Fragrance & Flavor – Art & Science  Rose oil – What’s Important CH3 Odor Unit = Concentration Odor Threshold Threshold in Odor Units -3 ppb x 10 40 9500 75 1860 300 233 750 37 820 29 30 400 20 600 6 2300 0.5 9200 50 82 200 8 0.009 156000 0.007 42860 Rel. % of odor units 4.3 0.8 0.1 0.016 0.013 0.18 0.27 1 4.1 0.036 0.003 70 19.2 OH H3C CH3 CH3 O H3C H3C CH3 O CH3 CH3 CH3 H3C CH3 O CH3 CH3 Component (-)-Citronellol C14 - C16 Paraffins Geraniol Nerol Phenethyl alcohol Eugenol methyl ether Eugenol Farnesol Linalool (-)-Rose oxide (-)-Carvone Rose furan beta-Damascenone beta-Ionone % of Oil 38 16 14 7 2.8 2.4 1.2 1.2 1.4 0.46 0.41 0.16 0.14 0.03
Slide 45: Fragrance & Flavor – Art & Science  Perfumery - The Image of an Artist Parfume de Campange by Guy Begin
Slide 46: Fragrance & Flavor – Art & Science  The Perfumer – An artist with a different palette
Slide 47: Fragrance & Flavor – Art & Science  Marketing- The Image The Allure of Perfume is popularized by marketing France - late 19th century Spain - 1903 France - circa 1935
Slide 48: Fragrance & Flavor – Art & Science  Marketing- The Image The Allure of Perfume is popularized by marketing Zica-Alexa - Year 2000
Slide 49: Fragrance & Flavor – Art & Science OLFACTION & GUSTATION Multidisciplinary Fields •Fragrances Perfume Soap/ Detergent /Air Fresheners / Aromatherapy •Flavors – Food Science Food Products Beverages Chewing Gum/ Mouthwash/ Pharmaceuticals Tobacco
Slide 50: Fragrance & Flavor – Art & Science OLFACTION & GUSTATION Multidisciplinary Fields •Chemistry/ Biology/ Physiology/ Psychology - Organic Chemistry – Synthetic, Molecular structure, Biochemistry, Molecular Biology, Genomics, Anatomy, Neuroscience, Bioinformatics - Analytical Chemistry – GC-MS analysis, Quality Assurance - Physical Chemistry – Emulsions, Light scattering, etc. - Psychological aspects of perception – other influences •Computer Science – for all of the above +
Slide 51: Fragrance & Flavor – Art & Science TASTE = GUSTATION Taste (Gustation) - sensitivity to substances in solution Taste Buds in epithelium of tongue, soft palate, pharynx, larynx and epiglottis. 2000-5000 taste buds in humans, but large variation.
Slide 52: Fragrance & Flavor – Art & Science TASTE = GUSTATION Until the mid 1990’s only 4 taste sensations were recognized: • Sweet – e.g. Sucrose, Aspartame • Sour – e.g. Citric acid, Phosphoric acid (H+ ions) • Bitter – e.g. Quinine • Salty – Sodium Chloride A 5th taste sensation called “Umani” is now recognized. Most common example is MSG (Monosodium glutamate) which enhances meat flavor.
Slide 53: Fragrance & Flavor – Art & Science SMELL = OLFACTION Smell (Olfaction) - sensitivity to substances in gaseous phase - a distant sense
Slide 54: Fragrance & Flavor – Art & Science How We Smell - Olfactory Region (Regio olfactoria) Odorants are volatile chemicals carried by inhaled air to the Regio olfactoria (olfactory epithelium) located in the roof of the two nasal cavities of the human nose, just below and between the eyes. The olfactory region of each of the two nasal passages in humans is a small area of about 2.5 square centimeters containing in total approximately 50 million primary sensory receptor cells.
Slide 55: Fragrance & Flavor – Art & Science  New Technology – How We Smell Olfactory Nerve Olfactory Tract Mitral Cell Olfactory Bulb Glomerulli Olfactory Nerve Filaments Cribiform (bone) Axons Olfactory Receptor Neurons Cilia in Mucosa Air and Odorant Molecules Olfactory Epithelium Mucosa The olfactory region consists of cilia projecting down out of the olfactory epithelium. The olfactory cilia are the sites where molecular reception with the odorant occurs and sensory transduction (i.e., transmission) starts.
Slide 56: Fragrance & Flavor – Art & Science  New Technology – Understanding Scent Elucidation of Olfactory G-Protein Receptor Structures - a result of Genome Research Different Views of G-Protein Receptor Structures 900+ Human Olfactory Receptor Genes Identified – D. Lancet ~600 Pseudogenes + ~300 Intact Genes
Slide 57: Fragrance & Flavor – Art & Science  New Technology – Understanding Scent Putative Binding cavity in Human OR1.04.06 derived using CastP
Slide 58: Fragrance & Flavor – Art & Science Computer Modeling of New Odorants Olfactophoric Model of Sandalwood Odorants Javanol (Yellow) vs. beta-Santalol (Blue)
Slide 59: Fragrance & Flavor – Art & Science  New Technology – Digital Scent Hardware and software platforms for incorporating scent into all forms of media... Peripheral devices that recreate thousands of scents on demand. Authoring tools for the creation of "scent scores" for movies, music, and interactive games. Software that plays scented media, such as videos, music and DVD's. Systems for transmitting scent with music and movies over the Internet. And…for the Perfumer & Flavorist – A new tool for composing creations.
Slide 60: Fragrance & Flavor – Art & Science Flavor Research The Proof is in the Pudding koch378 Chef’s and flavor application specialists determine use levels and food applications.