Fragrances, Flavors and Fragrances, Flavors and Food AdditivesFood Additives

Dr. AKM Shfiqul IslamDr. AKM Shfiqul Islam

School of Bioprocess EngineeringSchool of Bioprocess Engineering

University Malaysia Perlis (UniMAP)University Malaysia Perlis (UniMAP)

What is fragrances?What is fragrances?

Manufacturing of perfume, cologen and toilet Manufacturing of perfume, cologen and toilet water are collectively known as fragrances. water are collectively known as fragrances.

Perfume?Perfume?

PerfumePerfume takes its name from Latin word takes its name from Latin word perfumareperfumare, means to fill with smoke, means to fill with smoke

PerfumePerfume is a mixture of fragrant essential oils is a mixture of fragrant essential oils and aroma compounds, fixatives, and solvents and aroma compounds, fixatives, and solvents used to give the human body, objects, and used to give the human body, objects, and living spaces a pleasant smell.living spaces a pleasant smell.

Back HistoryBack History

It was used in incense burned in Egyptian templesThe It was used in incense burned in Egyptian templesThe incenses were mixtures of finely ground spices held incenses were mixtures of finely ground spices held together by myrrh or storaxtogether by myrrh or storax

Later on it was discovered that if certain spices or Later on it was discovered that if certain spices or flowers are steeps in fats or oil, the fat or oil would flowers are steeps in fats or oil, the fat or oil would retain certain odoriferous principle.retain certain odoriferous principle.

Avicenna, the Arabian physician, discovered the steam Avicenna, the Arabian physician, discovered the steam distillation of volatile oils. distillation of volatile oils.

Prior to Modern Era Prior to Modern Era

Perfumes manufacture were trained through Perfumes manufacture were trained through apprenticeship in the laboratories, working apprenticeship in the laboratories, working with traditional materials in well defined with traditional materials in well defined pattern pattern

They achieved skill in mixing blending of They achieved skill in mixing blending of different materialsdifferent materials

European EraEuropean Era

The returning Crusaders brought the The returning Crusaders brought the technology to Europe.technology to Europe.

Classical colognes are at least 200 years old Classical colognes are at least 200 years old having oriented in Cologne, Germany.having oriented in Cologne, Germany.

Modern EraModern Era

The manufacturing process undergone drastic The manufacturing process undergone drastic changes in the past quarter centuries.changes in the past quarter centuries.

Location of Olfactory EpitheliumLocation of Olfactory Epithelium

Quartz Crystal Smell SensorQuartz Crystal Smell Sensor

Lipids which is known as bioactive materials Gas chromatography stationary phase materials

with different polarity is used in GC analysis

Concentration levelsConcentration levels

Perfume oil is necessarily diluted with a Perfume oil is necessarily diluted with a solvent because undiluted oils (natural or solvent because undiluted oils (natural or synthetic) contain high concentrations of synthetic) contain high concentrations of volatile components that will likely result in volatile components that will likely result in allergic reactions and possibly injury when allergic reactions and possibly injury when applied directly to skin or clothing. applied directly to skin or clothing.

FormulationFormulation

The precise formulas of commercial perfumes The precise formulas of commercial perfumes are kept are kept secretsecret. Even if they were widely . Even if they were widely published, they would be dominated by such published, they would be dominated by such complex chemical procedures and ingredients complex chemical procedures and ingredients that they would be of little use in providing a that they would be of little use in providing a useful description of the useful description of the experienceexperience of a scent. of a scent.

Creation of acceptable Creation of acceptable fragrances fragrances

It require professional knowledgeIt require professional knowledge Use of available raw materials, both natural Use of available raw materials, both natural

and syntheticand synthetic Use of a variety of new types of products Use of a variety of new types of products

requiring fragrancesrequiring fragrances Innovations in packing, e.g., aerosol sprays, Innovations in packing, e.g., aerosol sprays,

perfume powders, cream sachets, gels, lotions, perfume powders, cream sachets, gels, lotions, and sticksand sticks

PerfumePerfume

A perfume is defined as any mixture of A perfume is defined as any mixture of pleasantly odorous incorporated in suitable pleasantly odorous incorporated in suitable vehicle. vehicle.

The finest modern perfumes are neither wholly The finest modern perfumes are neither wholly synthetics nor completely naturalsynthetics nor completely natural to reduce the price, and to reduce the price, and to introduce fragrances into the enchanting gamut to introduce fragrances into the enchanting gamut

at present availableat present available

Constituents of perfumesConstituents of perfumes

Constituents of perfumes are:Constituents of perfumes are: vehicles or solventsvehicles or solvents the fixatives, andthe fixatives, and odoriferous elementsodoriferous elements

Vehicles Vehicles

Solvents used for blending and holding Solvents used for blending and holding perfume materialsperfume materials e.g., ethyl alcohol and water at different ratios – e.g., ethyl alcohol and water at different ratios –

depend on solubility of the oils employeddepend on solubility of the oils employed It is volatile nature and helps to project the It is volatile nature and helps to project the

sent it carriessent it carries It is fairly inert to solute and not too irritating It is fairly inert to solute and not too irritating

to human skinto human skin

Fixatives Fixatives

Fixatives may be defined as substances of Fixatives may be defined as substances of lower volatility of the perfume oils, which lower volatility of the perfume oils, which retard and even up the rate of evaporation of retard and even up the rate of evaporation of the various odorous constituentsthe various odorous constituents animal secretionsanimal secretions resinous productsresinous products essential oils, and essential oils, and synthetic chemicalssynthetic chemicals

Animal FixativesAnimal Fixatives CivetCivet –soft fatty acid secretion of the perineal gland of –soft fatty acid secretion of the perineal gland of

civet catcivet cat MuskMusk – dried secretion of the preputial glands of male – dried secretion of the preputial glands of male

musk deer found in musk deer found in HimalayasHimalayas AmbergrisAmbergris – calculus, or secretion, developed by certain – calculus, or secretion, developed by certain

whales whales MuscMusc zibatazibata – extracted from glands of Louisiana muskrat. – extracted from glands of Louisiana muskrat.

About 90% of the unsaponifiable materials in the muskrat About 90% of the unsaponifiable materials in the muskrat gland consists of large, odorless cyclic acohols, which are gland consists of large, odorless cyclic acohols, which are converted to ketones.converted to ketones.

Resinous fixatives Resinous fixatives

Normal or pathological exudates from certain Normal or pathological exudates from certain plantsplants Hard resins – benzoin and gumsHard resins – benzoin and gums Soft resins – myrrh and labdanumSoft resins – myrrh and labdanum Moderately soft (balsams) – Peru balsam, tolu Moderately soft (balsams) – Peru balsam, tolu

balsam, copiaba and storaxbalsam, copiaba and storax Oily materials (oleoresins) – terpenes Oily materials (oleoresins) – terpenes

Essential oil fixatives Essential oil fixatives

A few essential oil are used for their fixative A few essential oil are used for their fixative properties as well as their odorproperties as well as their odor Clary sageClary sage VetiverVetiver PatchouliPatchouli OrrisOrris Sandalwood Sandalwood

Synthetic fixatives Synthetic fixatives These are replace of costly imported animal fixativesThese are replace of costly imported animal fixatives

Glyceryl diacetateGlyceryl diacetate Ethyl phthalate Ethyl phthalate Benzyl benzoateBenzyl benzoate Amyl benzoate Amyl benzoate Cinnamic alcohol estersCinnamic alcohol esters Cinnamic acid estersCinnamic acid esters Musk ketoneMusk ketone Musk ambretteMusk ambrette Vanillin Vanillin CourmarinCourmarin Indole Indole Skatole Skatole

Odorous substancesOdorous substances

Essential oilsEssential oils The essential oils may be defined as volatile, The essential oils may be defined as volatile,

odoriferous oils of vegetable originodoriferous oils of vegetable origin

Essential oilsEssential oils

Essential oils may be defined as volatile, Essential oils may be defined as volatile, odoriferous oils of vegetable origin. odoriferous oils of vegetable origin.

Essential oils are probably connected with Essential oils are probably connected with metabolism, fertilization, or protection from metabolism, fertilization, or protection from enemies. It found in buds, flowers, leaves, enemies. It found in buds, flowers, leaves, bark, stems, fruits, seeds, wood, roots and bark, stems, fruits, seeds, wood, roots and rhizomes. rhizomes.

In some trees in oleoresinous exudates.In some trees in oleoresinous exudates.

Essential oilsEssential oils

Essential oils are insoluble in water and Essential oils are insoluble in water and soluble in organic solvents, although enough soluble in organic solvents, although enough of the oil may dissolve in water to give an of the oil may dissolve in water to give an intense odor to the solution, e.g., rose water or intense odor to the solution, e.g., rose water or orange flavor water.orange flavor water.

Essential oilsEssential oils

The compounds occuring in essential oils areThe compounds occuring in essential oils are1.1. Esters – mainly of benzoic, salicylic, acetic and cinnamic acidsEsters – mainly of benzoic, salicylic, acetic and cinnamic acids2.2. Alcohols – Linalool, geraniol, citronellol, terpinol, menthol, borneolAlcohols – Linalool, geraniol, citronellol, terpinol, menthol, borneol3.3. Aldehydes – citral, citronellol, benzaldehyde, cinnamaldehyde, Aldehydes – citral, citronellol, benzaldehyde, cinnamaldehyde,

vanillinvanillin4.4. Acids – benzoic, cinnamic, myristic, isovaleric in the free stateAcids – benzoic, cinnamic, myristic, isovaleric in the free state5.5. Phenols – eugenol, thymol, carvacrolPhenols – eugenol, thymol, carvacrol6.6. Ketones – carvone, menthone, pulegone, irone, camphor, methyl Ketones – carvone, menthone, pulegone, irone, camphor, methyl

nonyl ketone, methyl hepteninenonyl ketone, methyl heptenine7.7. Esters – cineole, internal ether (eucalyptole), anethole, safroleEsters – cineole, internal ether (eucalyptole), anethole, safrole8.8. Lactones – coumarinLactones – coumarin9.9. Terpenes – camphene, pinene, limonene, phellandrene, cedreneTerpenes – camphene, pinene, limonene, phellandrene, cedrene10.10. Hydrocarbons – cymene, styrene (phenylethylene)Hydrocarbons – cymene, styrene (phenylethylene)

H3CC

O CH2 CH

CH3

CH3

O

H3CC

O

O-CH2(CH2)6CH3

CH3CH2C

O

O CH2CH

CH3

CH3

CH2

CH3CH2CH2C

O

O CH2CH3

Isoamyl acetateBanana

(Alarm pheromone of honeybee)

Octyl acetateOranges

H3CC

O

O-CH2CH2CH3 H3CC

O

O-CH2CH C

CH3

CH3

Propyl acetatePear

Isopentenyl acetate"Juicy Fruit"

CH3CH2CH2C

O

O CH3H3C

C

O

O-CH2

Isobutyl propionateRum

Ethyl butyratePineapple

Methyl butyrateApple

Benzyl acetatePeach

C

O

OCH3

OH

CH2C

O

OCH2CH3

Methyl SalicylateOil of Wintergreen

Ethyl phenylacetateHoney

FLAVORS AND FRAGRANCESFLAVORS AND FRAGRANCES

Extraction process Extraction process

ExpressionExpression DistillationDistillation Extraction with volatile solventsExtraction with volatile solvents EnfleurageEnfleurage MacerationMaceration Microwave extractionMicrowave extraction Supercritical solvent extractionSupercritical solvent extraction

Synthetic and semisynthetic process Synthetic and semisynthetic process in perfumes and flavors in perfumes and flavors

Most of the perfumes and flavors are being Most of the perfumes and flavors are being made by chemical synthetic proceduremade by chemical synthetic procedure

Some constituents are chemically synthesized Some constituents are chemically synthesized from an isolate or other natural starting from an isolate or other natural starting materials are classed as semisyntheticsmaterials are classed as semisynthetics

Synthesis of perfumes and Synthesis of perfumes and fragrancesfragrances

Condensation porcessCondensation porcessCoumarinCoumarin occurs in tonka beans and 65 other plants, occurs in tonka beans and 65 other plants,

but the economical source is the synthetic. It is but the economical source is the synthetic. It is employed as a fixative and enhancing agent for employed as a fixative and enhancing agent for essential oils and tobacco products and as a essential oils and tobacco products and as a masking agent for disagreeable odors in industrial masking agent for disagreeable odors in industrial products.products.

CHO

OH

CH3COONa

(CH3CO)2O

CH=CHCOONa

OH

CHC=O

CH

O

Salicylaldehyde Coumarin

Synthesis of perfumes and Synthesis of perfumes and fragrancesfragrances

EsterificationEsterification Amyl alcohol and acetic acid give isopropyl acetateAmyl alcohol and acetic acid give isopropyl acetate

HO

isoamyl alcohol

O

OH

acetic acid

O

O

isopentyl acetate

+

Synthesis of perfumes and Synthesis of perfumes and fragrancesfragrances

Grignard processGrignard process Phenylethyl alcohol has a roselike odor and occurs Phenylethyl alcohol has a roselike odor and occurs

in the volatile oils of rose, orange flowers and in the volatile oils of rose, orange flowers and others. It is a oily liquid and much used in perfume others. It is a oily liquid and much used in perfume formulationformulation

Synthesis of perfumes and Synthesis of perfumes and fragrancesfragrances

HydrogenationHydrogenation

Food AdditivesFood Additives

What are food additives?What are food additives? Any substance added to food that changes its Any substance added to food that changes its

characteristicscharacteristics "any substance the intended use which results or may "any substance the intended use which results or may

reasonably be expected to result-directly or indirectly-in reasonably be expected to result-directly or indirectly-in its becoming a component or otherwise affecting the its becoming a component or otherwise affecting the characteristics of any food." characteristics of any food."

These are used in the production, processing, These are used in the production, processing, treatment, packaging, transportation or storage of treatment, packaging, transportation or storage of food.food.

Additives Are Used To:Additives Are Used To:

1.1. Maintain product consistency Maintain product consistency

2.2. Improve or maintain nutritional valueImprove or maintain nutritional value

3.3. Maintain palatability and wholesomenessMaintain palatability and wholesomeness

4.4. Provide leavening or control Provide leavening or control acidity/alkalinityacidity/alkalinity

5.5. Enhance flavor or bring out a desired color Enhance flavor or bring out a desired color

Benefits of AdditivesBenefits of Additives

Safer and More Nutritious FoodsSafer and More Nutritious Foods Antimicrobials = prevent food poisoning from Antimicrobials = prevent food poisoning from

various bacteria and moldsvarious bacteria and molds Antioxidants = prevent the development of Antioxidants = prevent the development of

off-flavors, production of potentially toxic off-flavors, production of potentially toxic products, and maintain nutritional value of products, and maintain nutritional value of vitamins and lipidsvitamins and lipids

Vitamins = prevent nutritional deficienciesVitamins = prevent nutritional deficiencies

Benefits of AdditivesBenefits of Additives

Greater Choice of FoodsGreater Choice of Foods Increased development in convenience Increased development in convenience

foods, snack foods, low-calorie foods, foods, snack foods, low-calorie foods, exotic foods, and a variety of food exotic foods, and a variety of food substitutessubstitutes

Benefits of AdditivesBenefits of Additives

Lower-Priced FoodsLower-Priced Foods Total removal of additives would result in Total removal of additives would result in

higher priceshigher prices

Food AdditivesFood Additives

Food additives can be divided into several groups, Food additives can be divided into several groups, although there is some overlap between them.although there is some overlap between them.

Acids  Acids  Food acids are added to make flavors "sharper", and also Food acids are added to make flavors "sharper", and also

act as preservatives and antioxidants. Common food acids act as preservatives and antioxidants. Common food acids include vinegar, citric acid, tartaric acid, malic acid, include vinegar, citric acid, tartaric acid, malic acid, fumaric acid, lactic acid. fumaric acid, lactic acid.

Antioxidants  Antioxidants  Antioxidants such as vitamin C act as preservatives by Antioxidants such as vitamin C act as preservatives by

inhibiting the effects of oxygen on food, and can be inhibiting the effects of oxygen on food, and can be beneficial to health. beneficial to health.

Food coloring  Food coloring  Colorings are added to food to replace colors lost Colorings are added to food to replace colors lost

during preparation, or to make food look more during preparation, or to make food look more attractive. attractive.

Flavors  Flavors  Flavors are additives that give food a particular Flavors are additives that give food a particular

taste or smell, and may be derived from natural taste or smell, and may be derived from natural ingredients or created artificially. ingredients or created artificially.

Preservatives  Preservatives  Preservatives prevent or inhibit spoilage of food Preservatives prevent or inhibit spoilage of food

due to fungi, bacteria and other microorganisms. due to fungi, bacteria and other microorganisms. Sweeteners  Sweeteners 

Sweeteners are added to foods for flavoring. Sweeteners are added to foods for flavoring. Sweeteners other than sugar are added to keep the Sweeteners other than sugar are added to keep the food energy (calories) low, or because they have food energy (calories) low, or because they have beneficial effects for diabetes mellitus and tooth beneficial effects for diabetes mellitus and tooth decay and diarrhea. decay and diarrhea.