Food Flavor

Chapter 11 in your textbook

Intermolecular Copigmentation
OH

OH

HO

+
O HO O OH O

OH

HO

+
O HO O OH

OH

OH O OH O O OH

OH OH OH

Cyanidin-3--D-glucoside

Cyanidin-3-(6-O-p-coumaroyl-D-glucoside

Copigment Stacking
Co-Factor

Pigment

Co-Factor

Hyperchromic shift Bathochromic shift

Anthocyanin Color
The

poor stability of anthocyanins creates the need to modify stability or find new sources
Increase

color and oxidative stability

Abs

Result:

More red color at higher pH levels Greater application range in foods Enhanced antioxidant capacity; health benefits

l nm

Flavor Chemistry
Flavor is a combination of taste and aroma Taste - sweet, sour, bitter, salty - only what can be sensed on the tongue - nerve sensations for metallic and astringent Aroma - volatiles are released in mouth and then sensed in the nasal cavity

Sensory Impressions

Visual impression

Color, size, shape, luster Volatile, odor-active compounds Sweet, sour, bitter, salty Pain, burning, cold, warmth, astringent, fizzy

Odor

Taste

Somato-sensory

Trigeminal nerve response

Texture, resistance, elasticity Sounds

Modern Flavor Chemistry

Savory

Roast, Pan Dripping, Seared , Grilled , Braised, Au jus

Milk, cream, dairy, cheese, butter, sweet brown flavors, and dairly masking agents Natural, synthetic, WONF, enhancers, mimics, green, citrus, floral, tropical, exotic, complimentary Nutritionally enhanced/fortified, soy milks, tea, coffee, liqueurs, energy, fortified waters, dry drink bases, syrups

Diary

Fruit

Beverages

Sweet

Molecular Basis of Sweetness

-OH groups Acree and Shallenberger AH/B concept

Acree and Shallenberger

(Shallenberger & Acree) published a paper entitled the "Molecular Theory of Sweet Taste" in Nature [1969]. The model developed in that paper for sweetness was based on a structure-activity relationship between the simplest sweet tasting compounds and their structural features of the stimulants and has become known as the AH-B theory. The theory described with considerable success the structural features necessary for sweetness but it was not sufficient to predict sweetness. That is, not all compounds that satisfied the theory tasted sweet nor was the theory able to predict potency level especially for the very high potency sweetners subsequently synthesized. However, all sweet compounds seemed to have an identifiable AH-B feature.

AH/B Model

AH Weak acid, B - electronegative group

The perception of sweetness is proposed to be due to a chemical interaction that takes place on the tongue Between a tastant molecule and tongue receptor protein

THE AH/B THEORY OF SWEETNESS A sweet tastant molecule (i.e. glucose) is called the AH+/Bglycophore. It binds to the receptor B-/AH+ site through mechanisms that include H-bonding. Intermolecular, anti-parallel hydrogen-bonding interaction

AH+ / BB Glycophore

Hydrophobic interaction
AH

AH

Tongue receptor protein molecule For sweetness to be perceived, a molecule needs to have certain requirements. It must be soluble in the chemical environment of the receptor site on the tongue. It must also have a certain molecular shape that will allow it to bond to the receptor protein. Lastly, the sugar must have the proper electronic distribution. This electronic distribution is often referred to as the AH, B system. The present theory of sweetness is AH-B-X (or gamma). There are three basic components to a sweetener, and the three sites are often represented as a triangle.

Identifying the AH+ and Bregions of two sweet tastant molecules: glucose and saccharin.

Gamma () sites are relatively hydrophobic functional groups such as benzene rings, multiple CH2 groups, and CH3

Saccharin

Sweetn Low, The 1st artificial sweetener Accidentally found in 1879 by Remsen and Fahlberg Saccharin use increased during wars due to sugar rationing By 1917, common table-top sweetener in America Banned in 1977 due to safety issue 1991, withdrew ban, but with warning label 2000, removed warning label Intensely sweet, but slight bitter aftertaste

Aspartame

Nutrasweet, Equal Discovered in 1965 by J. Schlatter Composed of aspartic acid and phenylalanine 4 kcal/g, but 200 times sweeter Approved in 1981 for table-top sweetener and powdered mixes Safety debating 1996, approved for use in all foods and beverage Short shelf life, not stable at high temperature

Sucralose

Splenda 1998, approved for table-top sweetener and use in various foods Approved already in UK, Canada before US Only one made from sugar

There was a law suit last year of this claim Splenda lost.not a natural compound.a bit of a deceptive marketing.

Clean, sweet taste and no undesirable off-flavor

Acesulfame K

Sunette, Sweet One Discovered in 1967 by Hoechst 1992, approved for gum and dry foods 1998, approved for liquid use Blending with Aspartame due to synergistic effect Stable at high temperature and long shelf life (34 years) Bitter aftertaste

Neotame

Brand new approved sweetener (Jan. 2000) 7,000 ~ 13,000 times sweeter than sugar Dipeptide methyl ester derivative; structurally similar to Aspartame Enhance sweetness and flavor Baked goods, non-alcoholic beverages (including soft drinks), chewing gum, confections and frostings, frozen desserts, processed fruits and fruit juices, toppings and syrups. Safe for human consumption

Reb-A (diterpene glucoside)

http://www.reb-a.com/

Food flavors Mixtures of natural and/or artificial aromatic compounds designed to impart a flavor, modify a flavor, or mask an undesirable flavor Natural versus Artificial Natural - concentrated flavoring constituents derived from plant or animal sources

Artificial - substances used to impart flavor that are not derived from plant or animal sources

Most natural flavors are concentrated from botanicals -plants, trees, fruits, and vegetables

Most artificial flavors are synthesized with high purity - pharmaceutical flavors Isolation techniques - Steam distillation - mint and herbal oils - Solvent extraction - vanilla & oleoresins - Expression - citrus oils - Supercritical fluid extraction targeted extractions

Flavor Houses
Givaudan IFF Bell Flavors Wild Sensus Flavors Virginia Dare Blue Pacific

Natural flavors can also be enzymatically or chemically produced - Fermentation reactions - Microbial enzymes Saccharomyces Sp. Lactobacillus Sp. Bacillus Sp. Molds Maillard flavor compounds Glucose Glucose Glucose Glucose + + + + Glutamic acid = chicken Lysine = burnt or fried potato Methionine = cabbage Phenylalanine = caramel + + + + Glutamic acid Lysine Methionine Phenylalanine = = = = chicken fried potato bean soup wet dog

Fructose Fructose Fructose Fructose

Artificial Flavors
Typically are esters Esters have pleasant fruity aromas, derived from acids

a condensation reaction ACID + ALCOHOL --> ESTER + WATER Most artificial flavors are simple mixtures of esters i.e. Isobutyl formate + isobutyl acetate = raspberry

FERMENTATION and FLAVOR

O O
Diacetyl (CH3 C - C CH3 ) is a compound produced by

Yeasts via fermentation of carbohydrates Major compound in the flavor of cultured dairy products Butter and butter-like flavor Compounds potentially used for diacetyl formation
Lactic acid Pyruvic acid Oxalacetic acid acetyl lactic acid

Acetaldehyde

Citric acid

Flavor stabalization
- Need to protect from light, heat, oxygen, water

- Liquid flavors are typically dissolved in solvents

Partially hydrogenated oil or brominated vegetable oil

Ethanol, propylene glycol, glycerin

Dry flavors are typically encapsulated - Spray drying - Use of excipients

Plating - coat flavor onto sugar or salt

Extrusion - glassy sugar film

Inclusion complex - beta cyclodextrins

Secondary coatings - high melting temperature fat

Flavor interactions
pH, tartness of acids dependent on acid

Acidulant, the type of acid used influences intensity of other flavors

Carbohydrates, can bind flavor compounds, so less flavor may be needed at low sugar levels Sweeteners, sweetness can impact flavor intensity

Lipids, flavors partition, fat helps flavor impact

Protein, selective binding of flavor compounds

Flavors complex mixtures of many compounds

-Amyl, butyl, ethyl esters - Amyl acetate = sweet fruity/ banana/ pear - Amyl caproate = sharp fruity/ pineapple - Amyl formate = sweet/ fruity -Organic acids containing aldehydes , aromatic esters, alcohols, ketones - Acetic acid = vinegary - Propionic acid = sour milk - Butyric acid = buttery

- Green flavors - cis 3-hexenol = green leafy - trans 2-hexenal = green apple - Citrus flavors are mixtures of: - Aldehydes - Aromatic esters - Terpenes - Alcohols - Terpenes - Limonene = sweet citrus/ orange peel - Alpha pinene = warm resinous/ pine-like - Dipentene = fresh citrus/ lemon like

- Floral aldehydes - Citral = floral/ sweet/ lemon (Pledge) - Octanol = floral/ fatty/ orange-like
- Dairy flavors - chemical and enzymatic -Short chain fatty acids Aliphatic alcohols - propyl, butyl, octyl -Lactonones - large chain delta lactones -Aliphatic aldehydes -acetyldehyde, butyraldehyde

- Sulfides - dimethyl, butyl, dimethyl sulfides -Aliphatic esters - butyrates, laurates, valerates - Di-keytones - diacetyl, acetylpropionyl - Lactones - undecalactone (C11) = peach/ sweet - octalactone (C8) = cooked coconut/ sweet

Gamma-Octalactone http://www.iff.com/Ingredients.nsf/FragIngredients!OpenForm

Brown flavors - Caramelized, roasted or burnt character - Bread-yeast, caramel, chocolate, coffee, maple, peanut - Sweet brown compounds Vanillin = sweet/ chocolate-like Maltol = sweet/ malty/ brown (flavor enhancer) Di-hydrocoumarin = sweet/ caramel/ nutlike - Non-sweet brown compounds - Dimethyl pyrazine = nutty/roasted - 2,3,5 trimethyl pyrazine = chocolate/ roasted

Flavor Compounds Formation by Maillard Reaction

Reducing Sugars and -amino acids

N-glycosylamine or N-fructosylamine
1-Amino-1-deoxy-2-ketose (Amadori intermediate) or 2-Amino-2-deoxy-1-aldose (Heynes intermediate) H2S NH3
Furans Thiophenes Pyrroles

Reductones and Dehydroreductones

Retroaldol Reaction
Hydroxyacetone Hydroxyacetylaldehyde Acetoin Acetylaldehyde Pyrazines Pyridines Oxazoles Glyoxal Pyruvaldehyde Glycerolaldehyde

+ Amino Strecker Acids degradation

Strecker Aldehydes + CO2 + -aminoketone (Methional, NH3, H2S)

Heterocyclizaion
Thiazoles Pyrroles

- Woody compounds - Alpha lonone = woody/balsamic/violet/red raspberry -Beta lonone = woody/balsamic/black raspberry - Spicy compounds Cinnamic aldehyde = cinnamon Eugenol = cloves Thymol = thyme Zingerone = ginger oil Capsicum = peppers

- Sulfur compounds - Diallyl disulfide = garlic onion - Methyl mercaptan = natural gas - Methyl thio butyrate = sour milk

Sour

SOURNESS and sour taste is often thought of as acid However there is not a simple relationship between acid concentration (pH) and sourness Organic acids differ in sourness:
CITRIC ACID (0.05 N solution): fresh taste sensation LACTIC ACID (0.05 N solution): sour, tart PROPIONIC ACID (0.05 N solution): sour, cheesy ACETIC ACID (0.05 N solution): vinegar PHOSPHORIC ACID (0.05 N solution): intense MALIC ACID (0.05 N solution): green TARTARIC ACID (0.05 N solution): hard

Bitter

BITTERNESS cqn be attributed to several inorganics and organics

KI CsCl MgSO4
Certain amino acids and peptides (dipeptide leucine-leucine) Alkaloids derived from pyridine (N-containing 6-membered ring) and purines

A = caffeine (1, 3, 7 trimethylxanthine)

B = theobromine (from cacao)

GYCOSIDES are sugars that have been added to a natural compound. Grapefruits generally have a bitter taste to them. This is due to the flavonoid compound Naringin.

Naringin actually has 2 sugars (both glucose) as part of its structure.

Compound is still intensely bitter. Removal of these sugars with naringinase, will render the compound tasteless. Naringin is then converted to Naringinin. The de-bittering of grapefruit juice can be done, if desired. Where rutinoside is the sugar:

Salty

SALTY depends on the nature of the cation and anion in the ionic salt crystal structure; high molecular weight salts may be bitter; some salts may even exhibit sweetness Examples:

NaCl NaBr NaI KCl LiBr NaNO3 = salty KBr = salty + bitter

Lead acetate (toxic) = sweet

Trigeminal Response

HOTNESS (pungency) is characteristic of piperine in black pepper and capsicum in red pepper and gingerols in ginger

Cool is a characteristic of menthol Peppermint or mint oils

HO OMe eugenol
Spicy is a characteristic of eugenol Clove, nutmeg, cinnamon, bay leaf

OH

menthol

Aromas

Sources of Aromas in Food

Natural
Herbs

flavors

and spices (some enzymatic rxns) Fruits (biosynthesis during ripening)

Process

flavors

Browning

and Maillard Lipid oxidation Fermentation

Artificial
Single

flavors

compounds with character impact

Isoamyl acetate = bananna

Allium sp.
(onions, garlic, shallots, leeks)
S-(1-propenyl)-L-cysteine sulfoxide Allinase 1-propenyl sulfenic acid
Chemical rearrangement Chemical Rearrangement w/heat

Thiopropanal S-oxide (Tear maker)

Mercaptans (thios) Disulfides

Lipoxygenase Generated Flavors

COOH

B O2 lipoxygenase

green
COH hexenal

melon, cucumber
COH

nonadienal

Vanilla- an extracted flavor

Vanillin Seed pods of Planifolia (a tropical orchid)

Sunlight Flavor
Sunlight will induce oxidized flavor and sunlight flavor and hay-like flavor. Oxidized flavor Sunlight flavor: burnt and / or cabbage

Riboflavin (B2) Effect on Sunlight Flavor

Riboflavin is a catalyst for production of the sunlight flavor. 1) Milk protein and riboflavin
sunlight

sunlight flavor

2) Riboflavin increase in milk will increase the sunlight flavor 3) Riboflavin removal prevent the sunlight flavor

According to the TG Lee Website:

Studies at the Silliker Laboratories in Illinois, the University of Michigan, and other leading labs and universities concluded that both sunlight and the fluorescent lighting in stores could decrease the freshness and flavor of milk and the potency of vital vitamins in it. But this research also showed that the majority of natural and artificial light could be blocked by containers that were yellow instead of white.

Riboflavin Effect on Sunlight Flavor

Riboflavin is a catalyst for production of the sunlight flavor. 1) Milk protein and riboflavin
sunlight

sunlight flavor

2) Riboflavin increase in milk will increase the sunlight flavor 3) Riboflavin removal prevent the sunlight flavor