The Art & Science of Fragrance & Flavor Creation

The Art & Science of Fragrance & Flavor Creation

Society of Flavor Chemist’sDecember 4, 2003

John C. Leffingwell

Fragrance & Flavor – Art & Science Conventional Market View – U.S. $15 Billion

Worldwide MarketFlavors vs. Fragrances

Flavors49%

Fragrances51%

Fragrance & Flavor – Art & Science Conventional Market View – U.S. $15 Billion

Eastern Europe

5%

Middle East & Africa

6%

25% 32%

26%South America

6%

NorthAmerica

Asia-Pacific

WesternEurope

Fragrance & Flavor – Art & Science

Conventional Market View – U.S. $15 Billion

Flavor & Fragance Market excludingBranded Soft Drink Concentrates

Others - 35.4%

Sensient - 2.8% (US)

T. Hasegaawa - 2.5 % (JP)

Mane - 1.8% (FR)Takasago - 5.6% (JP)

8.6% - Symrise (DE)

9.1% - Firmenich (CH)

7.6% - Quest Int'l (NL)

12.8% - Givaudan (CH)

12% - International Flavors & Fragrances

(US)

Danisco - 1.7% (DK)

Fragrance & Flavor – Art & Science The Real Market – U.S. $30 Billion

Flavor & Fragrance MarketIncluding Branded Soft Drink Concentrates

3% 3%

16%

39%

39%

Coca-Cola

PepsicoFlavor &

Fragrance

Cadbury Schweppes

Other Branded Soft Drinks

Fragrance & Flavor – Art & Science Fragrance & Flavor - The shaping of history

Prehistory - Culinary & Fragrant Oils

Circa 7000 BC – Fragrant plants and spices infused in the fatty oils of Olive & Sesame for use as ointments

Earliest items of commerce were most likely spices, gums and other fragrant plants.

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.

3000 BC – Egyptians– when learning to write and make bricks, were already importing large quantities of myrrh.

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

Fragrance & Flavor – Art & Science The shaping of history - Egypt

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.

Fragrance & Flavor – Art & Science The shaping of history – Greece

Greek Perfume Urns

Leucippus and Democritus – Fathers of the Atomic Theory

Fragrance & Flavor – Art & Science The shaping of history – Greece circa 400 BC

Still of Democritus

The first firm documentary evidence of the distillation of essential oils is Herodotus' record of the method of distilling turpentine from 425 B.C.

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.

Theophrastus' 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.

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.

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.

Fragrance & Flavor – Art & Science The shaping of history – Rome

Former Tyco CEO Dennis KozlowskiToday’s Nero

Fragrance & Flavor – Art & Science The Modern Toga Party

"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

Fragrance & Flavor – Art & Science The shaping of history – Biblical TimesFragrance 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 gold-colored, fragrant ambergris).

Mary Prophetissa (Prophetissima) aka Maria the Jewess

Fragrance & Flavor – Art & Science The shaping of history – 1ST Century AD

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.

The tribokos

Mary Prophetissa (Prophetissima) aka Maria the Jewess

Fragrance & Flavor – Art & Science The shaping of history – 1ST Century AD

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

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.

Fragrance & Flavor – Art & Science The shaping of history – 10 -11th Century AD

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.

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.

Fragrance & Flavor – Art & Science The shaping of history – Marco Polo

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.

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.

Fragrance & Flavor – Art & Science The shaping of history – Influence of Spice Trade1497 - Vasco da Gama departs Lisbon Portugal to discover the sea passage to the distant spice Indies.1498 - 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.

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 porcelainAnd – 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.

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.

Fragrance & Flavor – Art & Science The shaping of history – Spice Wars

New York traded for Rhun – the best Nutmeg island

Quite A Trade


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”.

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.

Fragrance & Flavor – Art & Science The shaping of history – France & Perfume

Fragrance & Flavor – Art & Science Grasse France – The Center of Perfumery

Perfume Factory - Grasse

Lavender field near Grasse

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

Grasse - Chiris factory - early 20th centuryPreparing the frame with fat

Fragrance & Flavor – Art & Science The Production of Rose Oil

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 cinnamaldehyde1868 – 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.


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

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

The new partner – The Organic Chemist

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.

Nobel Prize in Chemistry 2001 - Ryoji Noyori


CH3

OH

CH3CH3

CH3

OH

CH3CH3


CH3

CH3CH2

CH2

CH3 CH3

CH2

CH3

CH3 CH3

CH2

OH

CH3

CH3 CH3

OH

CH3

CH3 CH3

OH

CH3

CH3 CH3

O

CH3

CH3 CH3

OHbeta-Pinene

Myrcene

Linalool

Geraniol Citronellol Citronellal

Menthol

CH3

CH3 CH3

CH2

O

OCH3

Linalyl Acetate

1950’s – Bain & Webb – Turpentine into Fragrance & Flavor

Fragrance & Flavor – Art & Science Gas Chromatography – Mass Spectrometry

GC-MS analysis Detective work

Distillation & extraction Volatiles from a living flower


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


Volatile Chemicals Identified in Foodstuffs

0

1000

2000

3000

4000

5000

6000

7000

8000

1963

1969

1974

1979

1984

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Fragrance & Flavor – Art & Science 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

Fragrance & Flavor – Art & Science Perfumery - The Image of an Artist

Parfume de Campange by Guy Begin

Fragrance & Flavor – Art & Science The Perfumer – An artist with a different palette

Fragrance & Flavor – Art & Science Marketing- The ImageThe Allure of Perfume is popularized by marketing

France - late 19th century France - circa 1935 Spain - 1903

Fragrance & Flavor – Art & Science Marketing- The ImageThe Allure of Perfume is popularized by marketing

Zica-Alexa - Year 2000


Multidisciplinary Fields

•Flavors – Food Science Food Products Beverages Chewing Gum/ Mouthwash/ Pharmaceuticals Tobacco

•Fragrances Perfume Soap/ Detergent /Air Fresheners / Aromatherapy

OLFACTION & GUSTATION


•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

OLFACTION & GUSTATION

Multidisciplinary Fields

•Computer Science – for all of the above +


Taste Buds in epithelium of tongue, soft palate, pharynx, larynx and epiglottis. 2000-5000 taste buds in humans, but large variation.

Taste (Gustation) - sensitivity to substances in solution

TASTE = GUSTATION


TASTE = GUSTATION

Until the mid 1990’s only 4 taste sensationswere recognized:

• Sweet – e.g. Sucrose, Aspartame• Sour – e.g. Citric acid, Phosphoric acid (H+ ions)• Bitter – e.g. Quinine• Salty – Sodium ChlorideA 5th taste sensation called “Umani” is now recognized. Most common example is MSG (Monosodium glutamate) which enhances meat flavor.


Smell (Olfaction) - sensitivity to substances in gaseous phase - a distant sense

SMELL = OLFACTION


How We Smell -

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.

Olfactory Region (Regio olfactoria)

Fragrance & Flavor – Art & Science New Technology – How We Smell

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.

Olfactory TractMitral Cell

Olfactory Nerve Olfactory Bulb

OlfactoryEpithelium

Mucosa

Air and

Odorant Molecules

Cilia in Mucosa

Olfactory Receptor Neurons

GlomerulliOlfactory Nerve Filaments

Cribiform (bone)

Axons

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

Putative Binding cavity in Human OR1.04.06 derived using CastP

New Technology – Understanding ScentFragrance & Flavor – Art & Science


Computer Modeling of New Odorants

Olfactophoric Model of Sandalwood OdorantsJavanol (Yellow) vs. beta-Santalol (Blue)

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.


The Proof is in the Pudding

Chef’s and flavor application specialistsdetermine use levels and food applications.

Flavor Research

The Art & Science of Fragrance & Flavor Creation

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