FOOD CHEMISTRY

FSTC 312/313, 3+1 Credits

 Instructor: Dr.Steve Talcott
 Office: 220F Centeq A
 Phone: 862-4056
 E-mail: [email protected]
Dimensions of Food Science and
Technology
•Food processing and manufacture
•Food preservation and packaging
•Food wholesomeness and safety
•Food quality evaluation
•Food distribution
•Consumer food preparation and use
Components of Food Science
 Food Chemistry
 Food Microbiology
 Food Processing
 Regulations
 Nutrition
 Others
Food Chemistry
 Basis of food science
 Water

 Carbohydrates

 Proteins

 Lipids

 Micronutrients

 Phytochemicals

 Food reactions and interactions

Some Examples of Food Chemistry
 Lipids in Peanuts
 Open jar of peanut butter = chemical
reaction in the oil phase
 Oxidation of the unsaturated fatty acids in
the peanut oil results in production of a
rancid odor.
 Peanut butter represents a special food
system called an emulsion
H H H H
C C C C Hydrocarbon chain
H H
oxygen
Solutions and Emulsions
 Solutions are homogeneous mixtures in which solute
particles are small enough to dissolve within solvent

Solute examples: salt, sugar, vitamin C, other small solid particles

Solute liquid examples: water, ethanol

Dispersions (colloidal dispersions) are mixtures in which

solutes do not dissolve (too large, polarity restrictions, etc)

Examples of colloids milk protein (casein)

egg white protein (albumen)
gelatin protein
pectin polysaccharide
MILK Ca and Mg (minerals)
 What is an emulsion?
Mixture of two immiscible liquids

oil
Surface tension acts to keep the liquids
H2O
from mixing

Result: oil “sits” on

top of the water phase

Stable food emulsions = addition of emulsifiers

lecithin, sucrose esters, MAG, DAG, etc

milk Margarine
O/W ice cream W/O butter

emulsion
mayo emulsion
Institute of Food Technologists
 Join IFT as a student member.

 www.ift.org

 Just do it.
 www.ift.org

IFT Definition of Food Science

Food science is the discipline in which biology,
chemistry, physical sciences and engineering are
used to study:
The nature of foods
The causes of their deterioration
The principles underlying food processing.
Food Science: An Interdisciplinary
Field of Study
Microbiology

Biology Chemistry

Food Science
Physics Nutrition
Engineering
The “Basics” of Food Chemistry
Foods Are Made of Chemicals
 Single
elements
 Chemically bonded elements (compounds)
Electrons Distributed via Energy Layers
Common Chemical Bonds in Foods
 Covalent
 Sharing 1 or more pairs of electrons
 Very strong bonds, not easily broken in foods
 C-C or C=C bonds
 Ionic
 Filling of orbitals through the transfer of electrons
 Cations (+) and Anions (-); Na+ + Cl- => NaCl
 Hydrogen
 Compounds containing O or N with bound hydrogen
 Very weak bonds; C-H or N-H
Functional Groups in Foods
 Exams and Grading
 3 hourly exams
 Material is not “cumulative”, but material will build
upon itself.
 Multiple choice, short answer, short essay format
 2 class assignments
 Short term paper
 Literature review
 Topic of special interest
 etc
 Several announced or unannounced quizzes
 Beginning or end of class
 University excused absence policy will be followed
Functional Groups in Foods
 SOME FOOD MOLECULES
important in food chemistry

H–O–H CH3 – COOH O=C=O

Na H CO3 C6H12O6 NaCl

NH2 – CH2 - COOH CH3 – (CH2)n - COOH

 A Few Food Functional Groups:

ACID GROUP: “carboxylic acid” COOH

acids donate (lose) protons

COOH  COO(-) + H(+)

This means acids form ions (charged species)
anion has (-) charge
cation has (+) charge

Vinegar contains acetic acid CH3COOH

Tartaric acid found in grapes is a di-carboxylic acid –

what does this mean?
Citric acid is tri-carboxylic acid.
AMINO GROUP: NH2
Derived from ammonia (NH3)

Amines are “basic” – means they gain protons

methyl amine: CH3 – NH2

trimethylamine is found in fish, and is responsible for

“fishy odor”

CH3 – CH – COOH Alanine, an amino acid

NH2
 Alcohol group - OH “hydroxyl group”

Methyl alcohol = methanol: CH3- OH

Ethanol C2H5OH is produced during the fermentation

of sugars; it is water-soluble and is called “grain alcohol”
because it is obtained from corn, wheat, rice, barley,
and fruits.

Yeasts use sugars for food – they ferment

simple carbohydrates and produce ethanol and CO2:

STARCH hydrolysis  C6H12O6  2 C2H5OH + 2 CO2

Glucose Ethanol Carbon
Dioxide
Other food molecules that contain OH groups: cholesterol (a lipid),
tocopherol (a vitamin), retinol (a vitamin), & calciferol (a vitamin)
Aldehyde group - CHO

There is actually a double bond between two atoms

in this group:

-C–H formaldehyde HCHO: H–C–H

O O

Aldehydes can be formed from lipid oxidation, and

generally have very low sensory thresholds.

For example, fresh pumpkin has the smell of

acetaldehyde; fresh cut grass the small of hexenal.
 We have already talked generally about covalent, ionic, and
hydrogen bonds:

Covalent: Sharing of electrons, strong bonds, C-C or C=C bonds

Ionic: Transfer of electrons, NaCl
Hydrogen: Weak bonds with O or N with bound hydrogen

There are 3 other important bonds in foods:

(1) An ester bond (linkage) in lipids

(2) A peptide bond (linkage) in proteins

(3) A glycosidic bond (linkage) in sugars

 An ester bond (linkage) in lipids:
In food fats, fatty acids are attached to glycerol molecules, through
what is called an ester linkage

O
Glycerol C O fatty acid

Ester linkage
“Acyl” linkage
Glycerol is a small molecule, containing only 3 carbons

But, to each carbon atom of glycerol, one fatty acid

can attach, via an ester bond.

A mono-, di-, or tri-esterified fatty acid to a glycerol is:

A MONOACYLGLYCEROL. A fat molecule that

has ONE fatty acid attached (“esterified”) to glycerol.

A DIACYLGLYCEROL. A fat molecule that

has TWO fatty acids esterified to glycerol.

A TRIACYLGLYCEROL. A fat molecule that

has THREE fatty acids esterified to glycerol.
 H
H O
H–C–OH
H – C – O – C - (CH2)n – CH3
H–C–OH
H–C–OH
H–C–OH “I’m a fatty acid chain”
H–C–OH
H
H

a monoglyceride

Glycerol
What do peptide bonds (linkages) in proteins look like?

In food proteins, or “polypeptides”, individual amino acids are

attached to each other through what is called a peptide linkage

Amino acid Amino acid. . . repeat

Peptide linkage
AMINO ACIDS contain both the amino (NH2)
and the acid (COOH) group in their structure.

In the formation of a peptide bond, one of the amino

acids loses one H atom, and the other loses O and H.

H O H O
NH2 C – C - O – H ------------- NH2 C – C - O – H

“R” “R”
R is any
Side chain

Acid group of the amino acid Amino group

The formation of peptide bond

N-C-C-N
A glycosidic linkage in sugars connects
sugar units into larger structures

Glycosidic linkage

glucose glucose
O

MALTOSE, a disaccharide composed of 2 glucose units

Structures of sugar disaccharides

Alpha 1,4 glycosidic

bond

Beta 1,4 glycosidic

bond

Alpha 1,4 glycosidic

bond
Polymeric Linkages

CH 2 OH CH 2 OH
O O

O OH O OH
OH OH
Amylose Cellulose
Alpha 1,4 Linkage Beta 1,4 Linkage
Digestible Indigestible
 Acids in Foods
Organic acids
 Citric (lemons), Malic (apples), Tartaric
(grapes), Lactic (yogurt), Acetic (vinegar)
 Food acids come in many forms, however:
 Proteins are made of amino acids
 Fats are made from fatty acids

 Fruits and vegetables contain phenolic acids

 Organic acids are characterized by carboxylic

acid group (R-COOH); not present in “mineral
acids” such as HCl and H3PO4
Chemical
Structures
of
Common
Organic
Acids
 Acids in Foods
 Add flavor, tartness
 Aid in food preservation by lowering pH
 Acids donate protons (H+) when dissociated
 Strong acids have a lot of dissociated ions
 Weak acids have a small dissociation constant
 Acids dissociate based on pH
 As the pH increases, acid will dissociate
 pKa is the pH equilibrium between assoc/dissoc
Titration Curve for Acetic Acid
 Acids in Foods
 Weak acids are commonly added to foods
 Citric acid is the most common
 When we eat a food containing citric acid, the
higher pH of our mouth (pH 7) will dissociate
the acid, and giving a characteristics sour flavor
pH and Titratable Acidity
 pH measures the amount of dissociated ions
 TA measures total acidity (assoc and dissoc)
 The type of food process is largely based on pH
 They also have other roles in food
 Control pH
 Preserve food (pH 4.6 is a critical value)
 Provide leavening (chemical leavening)
 Aid in gel formation (i.e. pectin gels)
 Help prevent non-enzymatic browning
 Help prevent enzymatic browning
 Synergists for antioxidants (for some, low pH is good)
 Chelate metal ions (i.e. citric acid)
 Enhance flavor (balance sweetness)
Acids in Foods
 In product development you can use one acid
or a combinations of acids

 -flavor
 -functionality
- synergy
 - Naturally occurring blends
 - Food additives
Acidity is important chemically

 -Denaturation and precipitiation of proteins

 -Modify carbohydrates and hydrolysis of

complex sugars

 -Hydrolysis of fatty acids from TAG’s

 Generally under alkaline conditions

 Inversion of sugars (sucrose to glu + fru)

Functional Groups and Bonds
 Acids
 Amino
 Alcohol
 Aldehydes

 Ester
 Peptide
 Glycosidic
 Application: Organic Acids
 Control pH
 Preserve food (pH 4.6 is a critical value)
 Provide leavening (chemical leavening)
 Aid in gel formation (i.e. pectin gels)
 Help prevent non-enzymatic browning
 Help prevent enzymatic browning
 Synergists for antioxidants (for some, low pH is good)
 Chelate metal ions (i.e. citric acid)
 Enhance flavor (balance sweetness)
Acidity is important chemically

 Denaturation and precipitiation of proteins

 Modify carbohydrates and hydrolysis of

complex sugars

 Hydrolysis of fatty acids from TAG’s

 Generally under alkaline conditions

 Inversion of sugars (sucrose to glu + fru)

Chemical Reactions in Foods
(1) Enzymatic
(2) Non-enzymatic

Generically applied to:

Carbohydrates
Lipids
Proteins
CARBOHYDRATE
chemical reactions:

 Enzymatic browning
 Non-enzymatic browning
 Hydrolysis
 Fermentation
 Oxidation/reduction
 Starch gelatinization
PROTEIN
chemical reactions:

 Buffering
 Non-enzymatic browning
 Hydrolysis
 Condensation
 Oxidation
 Denaturation
 Coagulation
LIPID
chemical reactions

 Oxidation
 Hydrolysis
 Hydrogenation
 Chemical Reactions in Foods
 Enzymatic
 Enzymes are proteins that occur in every living system
 Enzymes can have beneficial and detrimental effects
 Bacterial fermentations in cheese, pickles, yogurt
 Adverse color, texture, flavor, and odor

 High degree of specificity (Enzyme – Substrate)

 Non-enzymatic
 Those reactions that do not require enzymes
 Addition, redox, condensation, hydrolysis
The Active Site of the ES Complex
 Enzyme Reactions
 Enzymatic reactions can occur from enzymes
naturally present in a food
 Or as part of food processing, enzymes are
added to foods to enable a desired effect
 Enzymes speed up chemical reactions (good
or bad) and must be controlled by
monitoring time and temperature.
 Typically we think of enzymes as “breaking
apart” lipids, proteins, or carbs; but ther are
are several enzyme categories
sucrase
sucrose glucose + fructose
“invertase”
 Enzyme Class Characterizations
1. Oxidoreductase
1. Oxidation/reduction reactions
2. Transferase
1. Transfer of one molecule to another (i.e. functional groups)
3. Hydrolase
1. Catalyze bond breaking using water (ie. protease, lipase)
4. Lyase
1. Catalyze the formation of double bonds, often in
dehydration reations
5. Isomerase
1. Catalyze intramolecular rearrangement of molecules
6. Ligase
1. Catalyze covalent attachment of two substrate molecules
 Common Enzyme Reactions
(some reactions can also occur without enzymes)

HYDROLYSIS
 Food molecules split into smaller products, due to the
action of enzymes, or other catalysts (heat, acid) in the
presence of water

OXIDATION / REDUCTION:
 Reactions that cause changes in a food’s chemical
structures through the addition or removal of an
electron (hydrogen).
 Oxidation is the removal of an electron
 Reduction is the addition of an electron
 Oxidation vs Oxidized

 The removal of an electron is oxidation (redox reactions).

 When a food system is oxidized, oxygen is added to an active
binding site
 For example, the result of lipid oxidation is that the lipid may
become oxidized.

 In the food industry, we common speak of “oxidizing agents”

versus “reducing agents”. Both are used in foods.
 Reducing agents are compounds that can donate an electron in the
event of an oxidation reaction.
 L-ascorbic acid is an excellent reducing agent as are most antioxidants
 Oxidizing agents induce the removal of electrons
 Benzoyl peroxide is commonly added to “bleached” wheat flour
Enzymes
 Living organisms must be able to carry out chemical reactions
which are thermodynamically very unfavorable
 Break and/or form covalent bonds
 Alter large structures
 Effect three dimensional structure changes
 Regulate gene expression

They do so through enzyme catalysis

 A common biological reaction can take place without
enzyme catalysis
 …but will take 750,000,000 years
 With an enzyme….it takes ~22 milliseconds
 Even improvement of a factor of 1,000 would be good
 Only 750,000 years
 Living system would be impossible
 Effect of Enzymes
A bag of sugar can be stored for years with very little
conversion to CO2 and H2O
 This conversion is basic to life, for energy
 When consumed, it is converted to chemical energy
very fast
 Both enzymatic and non-enzymatic reactions

 Enzymes are highly specialized class of proteins:

 Specialized to perform specific chemical reactions
 Specialized to work in specific environments
 Enzymes
• Food quality can be changed due to the activity of
enzymes during storage or processing
• Enzymes can also be used as analytical indicators to
follow those changes

• Enzyme-catalyzed reactions can either enhance or

deteriorate food quality
• Changes in color, texture, sensory properties
 Enzyme Applications in the Food Industry

Carbohydrases: making corn syrup from starch

Proteases: Meat tenderizers
Lipases: Flavor production in chocolate and cheese

 Pectinases
 Glucose oxidase
 Flavor enzymes
 Lipoxygenase
 Polyphenol oxidase
 Rennin (chymosin)
 Food Quality

Food Chemistry and factors

influencing the foods we eat
 Overall Quality Factors
General Quality Factors
 Microbial safety first concern
 Prevent product tampering
 Nutritional quality
 Fat, protein, carbs, alcohol, vitamins, minerals,
fiber, phytochemicals, etc
 Storage stability
 How long will the product last?
 Standards of Quality
Quality standards
 FDA - mandatory (21 CFR)
 Minimum quality standards and standards of
identity
 Ice cream, mayonnaise, margarine, catsup
 USDA - optional
 Subjective evaluation of quality
 Beef: Prime, choice, select, standard, commercial,
utility, cutter, canner
 Quality Control
Quality control (QC)
 Lots and lots of jobs in the food industry in QC
 Insure quality of finished product by inspecting at
several important control points
 Raw materials
 In-line processing
 Final product
 Storage

 Chemical composition and understanding of

chemical reactions and mechanisms are vital to QC
 Quality Control
Quality control
 Objective testing for quality
 Such testing varies among food products
 Quality control charts - plot quality testing over time
 Establish control limits
100

Red = out of 80

control 60

Yellow = use 40
caution 20

Green = average 0
1 2 3 4 5 6 7 8
 Food Quality
Consumers judge quality using their senses
 Sight
 color, shape, obvious defects, etc.
 Taste
 Sweet, sour, bitter, salty
 Texture
 crispiness, smoothness, crunchy
 Appearance
Size and shape
 Size is easily measured
 Weight
 Count (per box)
 Visual look
 Automated sorters
 Shape is more difficult to measure
 Weights and Measures
1 bushel = 8 gallons
1 peck = ¼ bushel

 Apples (1 bushel) = 42-48#

 Blackberries (1 gallon) = 5-6#
 Blueberries (1 gallon) = 6-8#
 Grapes (1 bushel) = 44-55#
 Oranges (1 box) = 90#
 Grapefruit (1 box) = 85#
Appearance
Color
 Very important
 Several ways to measure
 Instrumental
 Sensory panel
 In this class…we will cover
 Browning reactions
 Natural and Certified colors
 Flavor
Flavor = Taste + Aroma
 4 tastes : sweet, sour, bitter, salty
 A 5th taste? .....…umami (taste “sensation”)
 Not all scientists are convinced that umami is a unique taste
 Some say the sensation caused by umami is simply a taste
enhancer
 Numerous odors (volatile, aroma-active compounds)
 We will examine some basic chemical parameters
influencing food flavor
 Toxicology
 Are there chemicals in our foods that are
harmful?
 What is the relationship between dose and a
harmful response?
 What is our responsibility to the public in the
food industry?
 Phytochemistry
 There are both nutrient and non-nutrient
compounds in our foods.
 Phyto = plant
 So a plant-based diet offers a diversity of
compounds that have no known use for
sustaining life.
 So why are these compounds important?
 If some of these compounds are ‘good’ for us,
then why don’t we say they are “essential”?
Food Additives
What does “GRAS” mean?

 Microbial inhibitors
 Antioxidants
 Sequestrants and chelating agents
 Emulsifiers
 Stabilizers and thickeners
 Bleaching and maturing agents
 pH control agents
 Food colors
 Sweeteners
 Flavoring agents
 Nitrites
Water
Water Content of Foods
 Tomatoes, lettuce -- 95%
 Apple juice, milk -- 87%
 Potato -- 78%
 Meats -- 65-70% H O
O H H
 Bread -- 35% H
 Honey -- 20%
 Rice, wheat flour -- 12%
 Shortening -- 0%
 Water Works
 Water must be “available” in foods for the action of
both chemical and enzymatic reactions.

 The “available” water represents the degree to which

water in a food is free for:
 Chemical reactions
 Enzymatic reactions
 Microbial growth
 Quality characteristics
 Related to a simple loss of moisture
 Related to gel breakdown
 Food texture (gain or loss)
 Water Works
 Very important (#1 ingredient in many foods)
 Structure
 Polar nature, hydrogen bonding
 Can occur in many forms (S,L,V)
 Acts as a dispersing medium or solvent
 Solubility
 Hydration
 Emulsions
 Gels
 Colloids
 Water Works
 The amount of “free” water, available for these reactions
and changes is represented by Water Activity.
 As the percentage of water in a food is “bound” changing
from its “free” state, the water activity decreases
 Water Activity is represented by the abbreviation: Aw
 Aw = P/ Po
 P = Vapor pressure of a food
 Po = Vapor pressure of pure water (1.0)
 Vapor pressure can be represented as equilibrium RH
 Is based on a scale of 0.0 to 1.0
 Any food substance added to water will lower water
activity….so, all foods have a water activity less than 1.0
 Water
Free vs. bound
 Water activity (Aw)
 Measured by vapor pressure of food
 This value is directly correlated to the growth of
microorganisms and the chemical reactions
 3 Forms of Water
 Free water (capillary water or Type III)
 Water that can be easily removed from a food
 Water that is responsible for the humidity of a food
 Water from which water activity is measured

 Bound water (adsorbed or Type II)

 Water that is tied up by the presense of soluble solids
 Salts, vitamins, carbohydrates, proteins, emsulifiers, etc.

 Water of hydration (Structured or Type I)

 Water held in hydrated chemicals
.
 Na2SO4 10H2O
 Water Sorption Isotherm
Type I Type II Type III
Hydration Absorbed Free

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Water Activity
Water Sorption Isotherm
Type I Type II Type III
Hydration Absorbed Free

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Water Activity
Moisture sorption isotherm (MSI)
 How to Use the Isotherm
Moisture sorption isotherms
 Shows the relationship between water activity and moisture at a
given temperature (the two are NOT equivalent)

 Represent moisture content at equilibrium for each water activity

 Allow for predictions in changes of moisture content and its

potential effect on water activity

 If the temperature is altered, then the relationships can not be

compared equivalently

 Each reaction is governed by its own temperature-dependence

 Acid hydrolysis reactions are faster at high temperatures
 Enzyme-catalyzed reactions cease to function at high temperatures
 Influences on Water Activity
 Foods will naturally equilibrate to a point of equilibrium with its environment
 Therefore, foods can adsorb or desorb water from the environment
 Desorption is when a “wet” food is placed in a dry environment
 Analogous to dehydration; but not the same
 Desorption implies that the food is attempting to move into equilibrium (ie. in a
package)
 Dehydration is the permanent loss of water from a food
 In both cases, the Aw decreases
 Desorption is generally a slow process, with moisture gradually decreasing
until it is in equilibrium with its environment.

 Adsorption is when a “dry” food is placed in a wet environment

 As foods gain moisture, the Aw increases
 The term “hygroscopic” is used to describe foods or chemicals that absorb
moisture
 A real problem in the food industry (lumping, clumping, increases rxn rates)
 Water Activity in Practice
 Bacterial growth and rapid deterioration
 High water activity in meat, milk, eggs,
fruits/veggies
 1.0-0.9

 Yeast and mold spoilage

 Intermediate water activity foods such as bread
and cheese
 0.75-0.9

 Analogous to a pH < 4.6, an Aw < 0.6 has the

same preservation effect
 Aw in Low Moisture Foods
 Water activity and its relationship with moisture content
help to predict and control the shelf life of foods.
 Generally speaking, the growth of most bacteria is
inhibited at water activities lower than 0.9 and yeast and
mold growth prevented between 0.80 and 0.88.
 Aw also controls physiochemical reactions.
 Water activity plays an important role in the
dehydration process. Knowledge of absorption and
desorption behavior is useful for designing drying
processes for foods.
 How to “Control” water
 The ratio of free to bound water has to be altered
 You can either remove water (dehydration or
concentration)
 Can change the physical nature of the food
 Alter is color, texture, and/or flavor
 Or you can convert the free water to bound water
 Addition of sugars, salts, or other water-soluble agents
 You can freeze the food
 This immobilizes the water (and lowers the Aw)
 However, not all foods can be or should be frozen
 Frozen foods will eventually thaw, and the problem persists
 Water
 Water contains intramolecular polar covalent bonds
 Effects
 Boiling point
 Freezing point
 Vapor pressure
 Easy formation of H bonds with food molecules
 Properties of Water
 The triple point is the temperature and pressure at
which three phases (liquid, ice, and vapor)
coexist at equilibrium, and will transform phases
small changes in temperature or pressure.
 The dashed line is the vapor pressure of
supercooled liquid water.
Chemical and functional properties of water
 Solvation, dispersion, hydration
 Water activity and moisture
 Water as a component of emulsions
 Water and heat transfer
 Water as an ingredient
Freezing
Greatly influenced the way we eat
 Freezing curves
 Water Freezes “Pure”
Frozen Foods
 Must be super-cooled to below 0°C
 Crystal nucleation begins
 Temperature rises to 0°C as ice forms
 Freezing Foods
40
35
Freezing Point
30
Temperature

25
20
Super-cooling
15
Latent heat of
10
Crystallization
5
0
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
Freezing Time
Freezing
Freezing Food
 Require lower temp. to continue freezing
 Last portion of water is very hard to freeze
 Unfrozen water is a problem
***As long as unfrozen water is present in a
food, the temperature will remain near 0°C
due to the latent heat of crystallization.
Freezing
Quality changes during freezing
 Concentration effect = small amount of
unfrozen water
 Excess solutes may precipitate
 Proteins may denature
 pH may decrease
 Gases may concentrate (i.e. oxygen)
Freezing
Quality changes during freezing
 Damage from ice crystals
 Puncture cell membranes
 Large crystals cause more problems
Fast freezing much more desirable
 Less concentration effect
 Smaller ice crystals
Freezing
Final storage temperature
 -18°C is standard
 Safe microbiologically
 Limits enzyme activity
 Non-enzymatic changes are slow
 Can maintain fairly easily
 Good overall shelf-life
Freezing
Intermittent thawing
 Partial thawing, then refreezing
 Complete thawing does not have to occur
 Get concentration effect
 Get larger ice crystals as water re-freezes
Freezing
Factors determining freezing rate:
 Food composition
 Fat and air have low thermal conductivity,
slow down freezing
 This is a “buffering” effect.
Freezing
Ways to speed up freezing
 Thinner foods freeze faster
 Greater air velocity
 More intimate contact with coolant
 Use refrigerant with greater heat capacity
 Freezing Foods
 Freezing can be damaging to food systems
 To reduce the chemical and mechanical damage to food systems
during freezing, technologies have been developed to freeze foods
faster or under high pressures. Benefits include:
 Higher density ice (less “space” between crystals from air or solids)
 Increased rate of freezing
 Smaller ice crystal formation
 Uniform crystal formation
 HP freezing generally involves cooling an unfrozen sample to
-21C under high pressures (300MPa) causing ice formation to
occur. 1 MPa ~ 145 psi or ~10 atm
 Another method involves pressure shift freezing where the food is
cooled under high pressures without causing freezing. Once the
pressure is released, the sample freezes instantly.
Dehydration and Concentration
of Foods

Controlling Water
 Dehydration and Concentration
Factors affecting drying rates
 Surface area
 Temperature
 Air velocity
 Humidity
 Pressure (vacuum)
 Solute concentration
 Amount of free and bound water
 Drying Curve of a Food
4.5
4
Water that is easily removed
Moisture Content

3.5
3
2.5
2
1.5 Water that is difficult to remove
1
0.5
0
0 1 2 3 4 5 6 7 8 9 10 11 12
Time (Hrs)
Dehydration and Concentration
Quality changes
Browning
 Enzymes - sulfite will prevent
 Carmelization - lower temps. will limit
 Maillard reaction - reaction of sugars and
amino acids - lower temps will limit
 Acrylamide…???

Flavor changes
Methods of Drying
Air drying methods
 Cabinet
 Tunnel
 Concurrent flow
 Countercurrent flow
 Continuous
 Fluidized bed
 Spray
 Drum
Carbohydrates
CARBOHYDRATES
Classifications for the main categories of food carbohydrates are
based on their degree of polymerization.
Types of Carbohydrates
 CARBOHYDRATES
 Carbohydrates are carbon compounds that contain many
hydroxyl groups.
 The simplest carbohydrates also contain either an aldehyde (these
are termed polyhydroxyaldehydes) or a ketone
(polyhydroxyketones).
 All carbohydrates can be classified as either monosaccharides,
disaccharides, oligosaccharides or polysaccharides.
 An oligosaccharide is anywhere from about two to ten
monosaccharide units, linked by glycosidic bonds.
 Polysaccharides are much larger, containing hundreds of
monosaccharide units.
 The presence of the hydroxyl groups (–OH) allows
carbohydrates to interact with the aqueous environment and to
participate in hydrogen bonding, both within and between chains.
 CARBOHYDRATES
 SUGARS contain 2 important and very reactive
Functional groups:
 -OH (hydroxyl group)
 Important for solubility and sweetness
 -C=O (carbonyl group)
 Important for reducing ability and Maillard browning

 GLUCOSE is an ALDOSE sugar with one C atom

external to the 6-membered ring

 FRUCTOSE is a KETOSE hexose with two carbon

atoms external to the 6-membered ring
 Monosaccharides
 The monosaccharides commonly found in
foods are classified according to the
number of carbons they contain in their
backbone structures.
 The major food monosaccharides contain
six carbon atoms.
Carbohydrate Classifications
 Hexose = six-carbon sugars
 Glucose, Galactose, Fructose
 Fischer Projection of a-D-Glucose

Haworth Projection of a-D-Glucose

Chair form of a-D-Glucose

 Disaccharides
 Bonds between sugar units are termed glycosidic bonds,
and the resultant molecules are glycosides.
 The linkage of two monosaccharides to form
disaccharides involves a glycosidic bond. The important
food disaccharides are sucrose, lactose, and maltose.

Sucrose: prevalent in sugar cane and sugar beets, is composed

of glucose and fructose through an α-(1,2) glycosidic bond.
Lactose:

is found exclusively in the milk of mammals and consists of

galactose and glucose in a β-(1,4) glycosidic bond.
Maltose:

Is the major degradation product of starch, and is composed

of 2 glucose monomers in an α-(1,4) glycosidic bond.
 Polysaccharides
 Most of the carbohydrates found in nature occur in the
form of high molecular weight polymers called
polysaccharides.
 The monomeric building blocks used to generate
polysaccharides can be varied; in all cases, however,
the predominant monosaccharide found in
polysaccharides is D-glucose.
 When polysaccharides are composed of a single
monosaccharide building block, they are termed
homopolysaccharides.
 Starch

 Starch is the major form of stored carbohydrate

in plant cells.
 Its structure is identical to glycogen, except for
a much lower degree of branching (about every
20-30 residues).
 Unbranched starch is called amylose
 Branched starch is called amylopectin.
FUNCTIONAL PROPERTIES OF CARBOHYDRATES

 Reducing sugars
 Browning reactions (caramelization and Maillard)
 Sweetness and flavors
 Crystallization
 Humectancy
 Inversion
 Oxidation and reduction
 Texturizing
 Viscosity
 Gelling (gums, pectins, other hydrocolloids)
 Gelatinization (Starch)
Aldose (aldehyde) and Ketose (ketone)
Properties of Glucose
 C1 of glucose is the carbonyl carbon
 Glucose has 4 chiral centers
 Non-super-imposable on its mirror image
 Carbons 2, 3, 4, 5 are chiral carbons

 The carbonyl carbon (C1) is also the site

of many reactions involving glucose
 They have two enantiomeric forms, D and
L, depending on the location of the
hydroxyl group at the chiral carbons.
Sugar Reactions
 Reduction of Monosaccharide
 In this reaction the carbonyl group is reduced to
an alcohol by a metal catalyzed reaction of
hydrogen gas under pressure.
Sugar Alcohols
Sugar Sweetness

 Not commonly found in nature Fructose 173

 Generally lower in calories (2 to 3 kcal/g) Sucrose 100
 A CHO for labeling purposes Xylitol 100
 Not digested by oral bacteria
Glucose 74
 “does not promote tooth decay”
Sorbitol 55
 – Xylitol (from xylose)
 – Sorbitol (from glucose)
Mannitol 50

 – Mannitol (from mannose) Maltose 32

 – Lactitol (from lactose) Lactose 15

 – Maltitol (from maltose)
 Sweetness is but one of a variety
of functional characteristics of
importance in food chemistry,
food product development, and
product quality

Functionality
FUNCTIONAL PROPERTIES OF CARBOHYDRATES

 Reducing sugars
 Browning reactions (caramelization and Maillard)
 Sweetness and flavors
 Crystallization
 Humectancy
 Inversion
 Oxidation and reduction
 Texturizing
 Viscosity
 Gelling (gums, pectins, other hydrocolloids)
 Gelatinization (Starch)
Sucrose

Where does sucrose come from?

Invert sugar
 Invert sugar is a liquid carbohydrate sweetener in which
all or a portion of the sucrose present has been inverted:
 The sucrose molecule is split and converts to an equimolar
mixture of glucose and fructose.
 Invert sugars have properties from sucrose; they help
baked goods retain moisture, and prolong shelf-life.
 Candy manufacturers use invert sugar to control
graining.
 Invert sugar is different from high fructose sweeteners

 SUCROSE + invertase enzyme  glucose + fructose

 Corn syrups
 Corn syrups are manufactured by treating corn starch
with acids or enzymes.
 Corn syrups, used extensively by the food industry and
in the home kitchen, contain primarily glucose
(dextrose) but other sugars as well.
 High-fructose corn syrup (HFCS) is made by treating
dextrose-rich corn syrup with enzymes (isomerase).
 The resulting HFCS is a liquid mixture of dextrose and
fructose used by food manufacturers in soft drinks,
canned fruits, jams and other foods.

 HFCS contains 42, 55, 90 or 99 percent fructose.

PROCESSING OF CORN STARCH  HFCS
 Corn starch is treated with α-amylase, of bacterial origin, to
produce shorter chains of sugars (dextrins) as starch fragments.

 Next, an enzyme called glucoamylase, obtained from the fungus

Aspergillus niger, breaks the fragments down even further to
yield the simple sugar glucose.

 A third enzyme, glucose isomerase, is expensive, and converts

glucose to varous amounts of frutose.
 HFCS-55 has the exact same sweetness intensity as sucrose (cola)
 HFCS-42 is less sweet, used with fruit-based beverages and for baking

 Glucose isomerase is so expensive that it is commonly

immobilized on a solid-based “resin” bead and the glucose syrup
passed over it. Can be used many times over before it slowly
looses its activity.
 HFCS
 HFCS is selected for different purposes.
Selection is based on specific desired properties:

 Retain moisture and/or prevent drying out

 Control crystallization
 Produce a higher osmotic pressure (more molecules in solution) than
for sucrose
 Control microbiological growth

 Provide a ready yeast-fermentable substrate

 Blend easily with sweeteners, acids, and flavorings
 Provide a controllable substrate for browning and Maillard reaction.
 Impart a degree of sweetness essentially = to invert liquid sugars

 High sweetness
 Low viscosity
 Reduced tendency toward crystallization
 Costs less than liquid sucrose or corn syrup blends
 Retain moisture and/or prevent drying out of food product
 HFCS
 HFCS has the exact same sweetness and taste as an equal
amount of sucrose from cane or beet sugar. Despite being a
more complicated process than the manufacture of sugar, HFCS
is actually less costly.
 It is also very easy to transport, being pumped into tanker
trucks.
 Two of the enzymes used, α-amylase and glucose-isomerase,
are genetically modified to make them more thermostable.
 This involves exchanging specific amino acids in the primary
sequence so that the enzyme is resistant to unfolding or
denaturing.
 This allows the industry to use the enzymes at higher
temperatures without loss of activity.
 Starches- #1 Hydrocolloid
 Hydrocolloids are substances that will form a gel or
add viscosity on addition of water.
 Most are polysaccharides and all interact with water.

 The most common is starch

 Starch is a mixture of amylose and amylopectin.

 The size distribution of these hydrocolloids is the most

important factor in the texture and physical features of
foods
 STARCH
Polymers of glucose
 AMYLOSE linear chain of glucose
 Glucose polymer linked α-1,4

 AMYLOPECTIN branched polymer of glucose

Amylose

Amylopectin
 AMYLOSE
 Linear polymer of glucose
 α 1 - 4 linkages
 Digestable by humans (4 kcal/g)
 250-350 glucose units on average
 Corn, wheat, and potato starch
 ~10-30% amylose
 AMYLOPECTIN
 Branched chain polymer of glucose
 α 1 - 4 and α 1 - 6 glycosidic linkages
 Fully digestable by humans
 1,000 glucose units is common
 Branch points every ~15-25 units
Starch

 Amylopectin (black)
 Amylose (blue)
 Modified Starches
 Gelatinization is the easiest modification
 Heated in water then dried.
 Acid and/heat will form “dextrins”
 α-Amylase
 hydrolyzes α (1-4) linkage
 random attack to make shorter chains
 β-Amylase
 Also attacks α (1 - 4) linkages
 Starts at the non-reducing end of the starch chain
 Gives short dextrins and maltose
 Both enzymes have trouble with α (1 - 6) linkages
DEXTRINS are considered to be hydrolysis products of
incompletely broken down starch fractions
 What’s the difference between…?
 Maltose
 Maltitol
 Maltodextrins
 Dextrins
 Dextrans

 Maltose = glucose disaccharide

 Maltitol = example of a “polyol”
 Maltodextrins = enzyme converted starch fragments

 Dextrins = starch fragments (α-1-4) linkages produced by

hydrolysis of amylose

 Dextrans = polysaccharides made by bacteria and yeast

metabolism, fragments with mostly α (1 - 6) linkages
Maltodextrins and enzyme-converted starch:

STARCH fermentation SUGARS

ETHANOL

MODIFIED STARCHES

GELATINIZED STARCH alpha amylase Maltodextrins

Corn Syrups

Sugars
The smaller the size of the products in these reactions, the
higher the dextrose equivalence (DE), and the sweeter
they are

Starch DE = 0
Glucose (dextrose) DE = 100

Maltodextrin (MD) DE is <20

Corn syrup solids (CS) DE is >20

Low DE syrup alpha amylase MD beta amylase High

DE
Syrup
 “Vegetable gum” polysaccharides are substances derived
from plants, including seaweed and various shrubs or trees,
have the ability to hold water, and often act as thickeners,
stabilizers, or gelling agents in various food products.

Plant gums - exudates, seeds

Marine hydrocolloids - extracts from seaweeds

Microbiological polysaccharides - exocellular polysaccharides

Modified, natural polysaccharides

 FUNCTIONS IN FOOD
 Gelatin
 Viscosity
 Suspension
 Emulsification and stability
 Whipping
 Freeze thaw protection
 Fiber (dietary fiber)
 Gut health
 Binds cholesterol
STRUCTURAL CONSIDERATIONS
 Electrical charge, pH sensitive
 Interactions with oppositely charged molecules
 Salts

 Low pH effects
 Chain length
 Longer chains are more viscous
 Linear vs Branched chains
 Inter-entangled, enter-woven molecules
 Gums
 GUAR (Guran Gum)
 Most used, behind starch, low cost
 Guar bean from India and Pakistan
 Cold water soluble, highly branched galactomannan
 Stable over large pH range, heat stable
 Thickening agent, not a gel
 Often added with xanthan gum (synergistic)
 XANTHAN
 Extracellular polysaccharide from Xanthomonas campestris
 Very popular, inexpensive from fermentations
 Forms very thick gels at very low concentrations
 Gums
 LOCUST BEAN
 Branched galactomannan polymer (like guar), but
needs hot water to solubilize
 Bean from Italy and Spain

 Jams, jellies, ice cream, mayonnaise

SEAWEED EXTRACTS
 Carrageenans (from red seaweed)
 Kappa (gel)
 Iota (gel)

 Lambda (thickener only)

 Milk, baking, cheese, ice cream

 Agar
 Alginates
 “Structural” Polysaccharides
Cellulose
 Polymer of glucose linked ß-1,4
Hemicellulose
 Similar to cellulose
 Consist of glucose and other monosaccharides
 Arabinose, xylose, other 5-carbon sugars
Pectin
 Polymer of galacturonic acid
 MODIFIED CELLULOSES
 Chemically modified cellulose
 Do not occur naturally in plants
 Similar to starch, but β-(1,4) glycosidic bonds
 Carboxymethyl cellulose (CMC) most common
 Acid treatment to add a methyl group
 Increases water solubility, thickening agent
 Sensitive to salts and low pH

 Fruit fillings, custards, processed cheeses, high

fiber filler
 PECTINS
 Linear polymers of galacturonic acid
 Gels form with degree of methylation of its carboxylic acid
groups
 Many sources, all natural, apple and citrus pomace
 Susceptible to degrading enzymes
 Polygalacturonase (depolymerize)
 Pectin esterases (remove methyl groups)
 Longer polymers, higher viscosity
 Lower methylation, lower viscosity
 Increase electrolytes (ie. metal cations), higher viscosity
 pH an soluble solids impact viscosity
PECTIC SUBSTANCES: cell cementing compound; fruits and vegetables;
pectin will form gel with appropriate concentration, amount of sugar and pH.

Basic unit comprised of galacturonic acid.

Composition: polymer of galacturonic acids; may be partially esterified.

Pectic Acid

Pectin Molecule
 Pectins
 Pectins are important because they form gels

 Mechanism of gel formation differs by the degree of esterification

(DE) of the pectin molecules
 DE refers to that percentage of pectin units with a methyl group attached

 Free COOH groups can crosslink with divalent cations

 Sugar and acid under certain conditions can contribute to gel

structure and formation

 LM pectin “low methoxyl pectin” has DE < 50% ; gelatin is

controlled by adding cations (like Ca++ and controlling the pH)

 HM pectin “high methoxyl pectin” has DE >50% and forms a gel

under acidic conditions by hydrophobic interactions and H-
bonding with dissolved solids (i.e. sugar)
Hydrophobic attractions between neighboring pectin polymer chains
promote gelation
 BETA-GLUCANS
 Extractsfrom the bran of barley and oats
 Long glucose chains with mixed ß-linkages
 Very large (~250,000 glucose units)
 Water soluble, but have a low viscosity
 Can be used as a fat replacer

 Responsible for the health claims (cholesterol) for

whole oat products
 Formulated to reduce the glycemic index of a food
 Others
CHITIN
 Polymer of N-Acetyl-D-glucosamine
 Found in the exoskeleton of insects and shellfish
 Many uses in industry, food and non-food.

INULIN
 Chains of fructose that end in a glucose molecule
 Generally a sweet taste
 Isolated from Jerusalem artichokes and chicory
 Act as a dietary fiber
 Potentially a pre-biotic compound
 COMPONENTS OF DIETARY FIBER

SOURCE
COMPONENT
Cellulose All food plants

All food plants, especially cereal

Hemicellulose
bran

Pectin Mainly fruit

Mainly cereals and 'woody'

Lignin
vegetables

Gums and some food Food additives in processed

thickeners foods
 HYDROCOLLOIDS
 A key attribute of gums is to produce viscous dispersions in water

 Viscosity depends on:

 Gum type
 Temperature
 Concentration of gum
 Degree of polymerization of gum
 Linear or branched polymers
 Presence of other substances in the system

 Solubility (dispersability in water) varies among gums

 Agar is insoluble in cold water; dissolves in boiling water

 Methylcellulose is insoluble in hot water, but soluble in cold !

BROWNING REACTIONS in CARBOHYDRATES

 There are 2 different kinds of browning reactions with carbohydrates:

 Caramelization

 Maillard (or non-enzymatic) browning

 CARAMELIZATION occurs when sucrose is heated >150-170°C (high

heat!) via controlled thermal processing
 Dehydration of the sugar, removal of a water molecule

 The structure of caramelized sugar is poorly understood but can exist in both
(+) and (-) species
 Commonly used as a colorant

 (+) charged caramel = promotes brown color in brewing and baking

industries

 (-) charged caramel in beverage/ soft drink industry (cola and root beer)
 CARAMELIZATION
 What is referred to as “caramel pigment” consists of a
complex mixture of polymers and fragments of
indefinite chemical composition
 Caramelans (24, 36, or 125 carbon lengths)
 Since caramel is a charged molecule, to be compatible
with phosphoric acid in colas the negative form is used

 Caramel flavor is also due to these and other fragments,

condensation, and dehydration products.
 diacetyl, formic acid, hydroxy dimethylfuranone
 Gums
 GUAR (Guran Gum)
 Most used, Cold water soluble, Stable, Thickening agent
 XANTHAN
 Polysaccharide from Xanthomonas campestris
 Popular, inexpensive
 Thick gels
 LOCUST BEAN
 Hot water to soluble
 Jellies, ice cream, mayonnaise
 PECTINS
 Linear polymers of galacturonic acid
 Gels form with degree of methylation of its carboxylic acid
groups
 Many sources, all natural, apple and citrus pomace
 Susceptible to degrading enzymes
 Polygalacturonase (depolymerize)
 Pectin esterases (remove methyl groups)
 Longer polymers, higher viscosity
 Lower methylation, lower viscosity
 Increase electrolytes (ie. metal cations), higher viscosity
 pH an soluble solids impact viscosity
Hydrophobic attractions between neighboring pectin polymer chains
promote gelation
 BETA-GLUCANS
 Extractsfrom the bran of barley and oats
 Long glucose chains with mixed ß-linkages
 Very large (~250,000 glucose units)
 Water soluble, but have a low viscosity
 Can be used as a fat replacer

 Responsible for the health claims (cholesterol) for

whole oat products
 Formulated to reduce the glycemic index of a food
 Others
CHITIN
 Polymer of N-Acetyl-D-glucosamine
 Found in the exoskeleton of insects and shellfish
 Many uses in industry, food and non-food.

INULIN
 Chains of fructose that end in a glucose molecule
 Generally a sweet taste
 Isolated from Jerusalem artichokes and chicory
 Act as a dietary fiber
 Potentially a pre-biotic compound
 COMPONENTS OF DIETARY FIBER

SOURCE
COMPONENT
Cellulose All food plants

All food plants, especially cereal

Hemicellulose
bran

Pectin Mainly fruit

Mainly cereals and 'woody'

Lignin
vegetables

Gums and some food Food additives in processed

thickeners foods
 HYDROCOLLOIDS
 A key attribute of gums is to produce viscous dispersions in water

 Viscosity depends on:

 Gum type
 Temperature
 Concentration of gum
 Degree of polymerization of gum
 Linear or branched polymers
 Presence of other substances in the system

 Solubility (dispersability in water) varies among gums

 Agar is insoluble in cold water; dissolves in boiling water

 Methylcellulose is insoluble in hot water, but soluble in cold !

 Wheat
Bran Corn
Removed

Milled,
Whole Polished
Wheat Rice
 Cereals
Cereals
 Starch, protein, fiber
 Water
 Lysine
 Structure
 Husk (inedible)
 Bran (fiber)

 Endosperm (starch, protein, oil)

 Germ (oil)
Wheat Kernel

Endosperm
Endosperm
Starch
Protein
Bran
Bran
Oil
Fiber

Germ
Germ
Oil
Protein
Cereal Grain
 Composition of Cereals
Grain Water Carbo. Protein Fat Fiber
Corn 11 72 10 4 2
Wheat 11 69 13 2 3
Oats 13 58 10 5 10
Sorghum 11 70 12 4 2
Barley 14 63 12 2 6
Rye 11 71 12 2 2
Rice 11 65 8 2 9
Buckwheat 10 64 11 2 11
Wheat
2 types of wheat
 HARD = higher protein (gluten), makes
elastic dough, used for bread-making
 Higher“quality”
 High water absorption

 SOFT = lower protein (gluten), make weak

doughs/batters, used for cakes, pastries,
biscuits, cakes, crackers, etc.
 Lower “quality” due to lower protein content
and useful applications
Wheat
Wheat Milling
To produce flour
 Cleaned with air (dust, bugs, chaff)
 Soaked to 17% moisture - optimum for
milling
 Remove husk
 Crack seeds - frees germ from endosperm
 Wheat
Wheat Milling
 Rollers- two metal wheels turning in opposite
direction of each other
 Endosperm is brittle and breaks
 Germ and bran form flat flakes and are
removed by screens or sieves
 Endosperm = flour
 Less color and less nutrients as milling continues
 Whole wheat flour = do not remove all of the
bran and/or germ
Wheat Mill Grinding Rolls
Wheat Milling Sifters
Wheat
Wheat Enrichment
 Add B-vitamins and some minerals to most
white flours (since missing the bran)
Uses of flour
 Cakes, breads, etc.
 Pasta, noodles, etc.
 Course flour, not leavened
Rice Processing
 Rice
Rice Milling
 Most rice is "whole grain"
 Remove husk, bran, germ by rubbing with
abrasive disks or rubber belts
 Polish endosperm to glassy finish
 Brown rice = very little milling
 Rice

Rice Enrichment
 Add some vitamins, minerals
 Coat rice with nutrients (folic acid)
Parboiling or steeping (converted rice)
 Boil rice before milling (~10 hrs, 70°C)
 Nutrients, vitamins and minerals, will
migrate into endosperm (no fortification)
 Rice

Rice
Other rice products
 Quick cooking (instant) = precooked, dried
 Rice flour
 Sake (15-20% alcohol)
Advantages/Disadvantages of
Milling Rice
 Brown Rice
 Minimal milling
 Higher in lipid (shortens shelf-life)
 Higher in minerals (not removed in milling)

 White (Milled) Rice

 Extreme milling
 Vitamins and minerals removed (Thiamin)
 Fortification to prevent Beriberi disease
Anatomy of Corn
Corn
Corn
 Some fresh/frozen/canned corn, but most is milled
 Dry milling (grits, meal, flour)
 Adjust moisture to 21%- optimum for "dry" milling
 Loosen hull (pericarp) and germ by rollers
 Dry to 15% moisture
 Remove husk with air blast; germ and bran by sieving
 Continue grinding endosperm to grits, meal or flour
 Process very similar to wheat milling at this point.
 Grits = large particle size
 Meal = medium particle size
 Flout = small particle size
Grain Processing
Wet milling (corn starch, corn syrups)
 Soak corn
 Grind with water into a wet "paste"
 Slurry is allowed to settle and the germ
and hulls float to top (high in oil)
 Remainder is endosperm (starch/protein)
 Centrifuged or filtered
 to remove/collect the starch
Grain Processing
Wet milling (cont'd.)
 Dried starch = corn starch
 Can produce corn syrups from starch
 Use enzymes (amylase) to break starch into
glucose (corn syrup)
 Use another enzyme (isomerase) to convert
glucose into fructose (HFCS)
 Can also produce ethanol from corn syrup
Products from Corn
 Grain Usage
Other grains- mostly for animal feed
 Barley = used in beer
 Rye = can not use alone (poor protein quality)
 Oats = oatmeal, flakes

Breakfast cereals
 Made from many different grains
Lipids
 Lipids
Main functions of lipids in foods
 Energy and maintain human health
 Influence on food flavor
 Fattyacids impart flavor
 Lipids carry flavors/nutrients

 Influence on food texture

 Solids or liquids at room temperature
 Change with changing temperature
 Participation in emulsions
 Lipids
 Lipids are soluble in many organic solvents
 Ethers(n-alkanes)
 Alcohols

 Benzene

 DMSO (dimethyl sulfoxide)

 They are generally NOT soluble in water

 C, H, O and sometimes P, N, S
 Lipids
 Neutral Lipids
 Triacylglycerols
 Waxes
 Long-chain alcohols (20+ carbons in length)
 Cholesterol esters
 Vitamin A esters
 Vitamin D esters
 Conjugated Lipids
 Phospholipids, glycolipids, sulfolipids
 “Derived” Lipids
 Fatty acids, fatty alcohols/aldehydes, hydrocarbons
 Fat-soluble vitamins
Lipids
Structure
 Triglycerides or triacylglycerols
 Glycerol + 3 fatty acids
 >20 different fatty acids
Lipids 101-What are we talking about?

 Fatty acids- the building block of fats

 A fat with no double bonds in it’s structure is said to
be “saturated” (with hydrogen)
 Fats with double bonds are referred to as mono-, di-,
or tri- Unsaturated, referring to the number of
double bonds. Some fish oils may have 4 or 5
double bonds (polyunsat).
 Fats are named based on carbon number and number
of double bonds (16:0, 16:1, 18:2 etc)
Lipids
 Oil- liquid triacylglycerides “Oleins”
 Fat- solid or semi-solid mixtures of crystalline
and liquid TAG’s “Stearins”
 Lipid content, physical properties, and
preservation are all highly important areas for
food research, analysis, and product
development.
 Many preservation and packaging schemes are
aimed at prevention of lipid oxidation.
 Nomenclature
 The first letter C represents Carbon
 The number after C and before the colon
indicates the Number of Carbons
 The letter after the colon shows the Number of
Double Bonds
 ·The letter n (or w) and the last number indicate
the Position of the Double Bonds
Saturated Fatty Acids
Mono-Unsaturated Fatty Acids
Poly-Unsaturated Fatty Acids
 Lipids
Properties depend on structure
 Length of fatty acids (# of carbons)
 Short chains will be liquid, even if saturated (C4 to C10)
 Position of fatty acids (1st, 2nd, 3rd)
 Degree of unsaturation:
 Double bonds tend to make them a liquid oil
 Hydrogenation: tends to make a solid fat
 Unsaturated fats oxidize faster
 Preventing lipid oxidation is a constant battle in the
food industry
Lipids 101-What are we talking about?

 Fattyacid profile- quantitative determination of the

amount and type of fatty acids present following
hydrolysis.
 To help orient ourselves, we start counting the
number of carbons starting with “1” at the
carboxylic acid end.
O
C C C C C C C C C C C C C C C C C C
18 1
OH
Lipids 101-What are we talking about?

 For
the “18-series” (18:0, 18:1, 18:2, 18:3) the
double bonds are usually located between carbons
6=7 9=10 12=13 15=16.
O
C C C C C C C C C C C C C C C C C C
18 16 15 13 12 10 9 1
OH
Lipids 101-What are we talking about?
 The biomedical field entered the picture and ruined
what food scientists have been doing for years with
the OMEGA (w) system (or “n” fatty acids).
 With this system, you count just the opposite.
 Begin counting with the methyl end
 Now the 15=16 double bond is a 3=4 double bond or
as the biomedical folks call it….an w-3 fatty acid
C
C C C C C C C C C C C C C C C C C C
1 3 4 6 7 9 10 18
OH
Melting Points of Lipids
 Tuning Fork Analogy-TAG’s
 Envision a Triacylglyceride as a loosely-jointed E
 Now, pick up the compound by the middle chain,
allowing the bottom chain to hang downward in a
straight line.
 The top chain will then curve forward and form an
h
 Thus the “tuning fork” shape
 Fats will tilt and twist to this lowest free energy
level
 Lipids
 Lipids are categorized into two broad classes.

 The first, simple lipids, upon hydrolysis, yield up to two types

of primary products, i.e., a glycerol molecule and fatty acid(s).

 The other, complex lipids, yields three or more primary

hydrolysis products.

 Most complex lipids are either glycerophospholipids, or

simply phospholipids
 contain a polar phosphorus moiety and a glycerol backbone
 or glycolipids, which contain a polar carbohydrate moiety
instead of phosphorus.
Lipids
 Other types of lipids
Phospholipids
 Structure similar to triacylglycerol
 High in vegetable oil
 Egg yolks
 Act as emulsifiers
 H
O
Fats and Oils… H C O C Fatty Acid Chain
can also be converted
H C OH
to an emulsifier…
H C OH

Production of mono- and diglycerides H

 Use as Emulsifiers
 Heat fat or oil to ~200°C

 Add glycerol and alkali

 Free Fatty Acids will be added to the glycerol

Fats and Oils: Processing
Peanut

Extraction
Rape Seed
 Rendering
 Pressing oilseeds
 Solvent extraction Safflower

Soybean Sesame
 Fats and Oils
Further Processing
 Degumming
 Remove phospholipids with water
 Refining/Neutralization
 Remove free fatty acids (alkali +
Oil water)
Refining  Bleaching
 Remove pigments (charcoal filters)
 Deodorization
 Remove off-odors (steam, vacuum)
 Where Do We Get Fats and Oils?
Neutralization
 Free fatty acids, phospholipids, pigments, and waxes exist in the crude oil
 These may promote lipid oxidation and off-flavors
 Removed by heating fats and adding caustic soda (sodium hydroxide) or soda
ash (sodium carbonate).
 Impurities settle to the bottom and are drawn off.
 The refined oils are lighter in color, less viscous, and more susceptible to
oxidation.

Bleaching
 The removal of color materials in the oil.
 Heated oil can be treated with diatomaceous earth, activated carbon, or
activated clays.
 Colored impurities include chlorophyll and carotenoids
 Bleaching can promote lipid oxidation since some natural antioxidants are
removed.
 Where Do We Get Fats and Oils?
Deodorization
 Deodorization is the final step in the refining of oils.
 Steam distillation under reduced pressure (vacuum).
 Conducted at high temperatures of 235 - 250ºC.
 Volatile compounds with undesirable odors and tastes
can be removed.
 The resultant oil is referred to as "refined" and is ready
to be consumed.
 About 0.01% citric acid may be added to inactivate pro-
oxidant metals.
 Where Do We Get Fats and Oils?
 Rendering
 Primarily for extracting oils from animal tissues.
 Oil-bearing tissues are chopped into small pieces and
boiled in water.
 The oil floats to the surface of the water and skimmed.
 Water, carbohydrates, proteins, and phospholipids
remain in the aqueous phase and are removed from the
oil.
 Degumming may be performed to remove excess
phospholipids.
 Remaining proteins are often used as animal feeds or
fertilizers.
 Where Do We Get Fats and Oils?
 Mechanical Pressing
 Mechanical pressing is often used to extract oil from
seeds and nuts with oil >50%.
 Prior to pressing, seed kernels or meats are ground into
small sized to rupture cellular structures.
 The coarse meal is then heated (optional) and pressed in
hydraulic or screw presses to extract the oil.
 Olive oils is commonly cold pressed to get virgin or
extra virgin olive oil. It contains the least amount of
impurities and is often edible without further processing.
 Some oilseeds are first pressed or placed into a screw-
press to remove a large proportion of the oil before
solvent extraction.
 Where Do We Get Fats and Oils?
 Solvent Extraction
 Organic solvents such as petroleum ether, hexane, and 2-propanol can be added
to ground or flaked oilseeds to recover oil.
 The solvent is separated from the meal, and evaporated from the oil.
Neutralization
 Free fatty acids, phospholipids, pigments, and waxes exist in the crude oil
 These promote lipid oxidation and off-flavors
 Removed by heating fats and adding caustic soda (sodium hydroxide) or soda
ash (sodium carbonate).
 Impurities settle to the bottom and are drawn off.
 The refined oils are lighter in color, less viscous, and more susceptible to
oxidation.
Bleaching
 The removal of color materials in the oil.
 Heated oil can be treated with diatomaceous earth, activated carbon, or
activated clays.
 Colored impurities include chlorophyll and carotenoids
 Bleaching can promote lipid oxidation since some natural antioxidants are
removed.
Hydrogenating Vegetable oils can
produce trans-fats
H H
C C
Cis-

H
C C
Trans-
H
http://www.foodnavigator-usa.com/Regulation/Trans-fats-Partially-hydrogenated-oils-should-be-phased-
out-in-months-not-years-says-expert-as-FDA-considers-revoking-their-GRAS-status
The cis- and trans- forms of a fatty acid
 Effects of Lipid Oxidation
 Flavor and Quality Loss
 Rancid flavor
 Alteration of color and texture
 Decreased consumer acceptance
 Financial loss
 Nutritional Quality Loss
 Oxidation of essential fatty acids
 Loss of fat-soluble vitamins
 Health Risks
 Development of potentially toxic compounds
 Development of coronary heart disease
 Simplified scheme of lipoxidation

H H H H H H H H
H H H H
R C C C C R R C C C C R
R C C C C R
H H O
H H + Catalyst * + Oxygen
O
LIPID OXIDATION and Antioxidants
 Fats are susceptible to hydrolyis (heat, acid, or lipase enzymes)
as well as oxidation. In each case, the end result can be
RANCIDITY.
 For oxidative rancidity to occur, molecular oxygen from the
environment must interact with UNSATURATED fatty acids in
a food.
 The product is called a peroxide radical, which can combine with
H to produce a hydroperoxide radical.

 The chemical process of oxidative rancidity involves a series of

steps, typically referred to as:
 Initiation
 Propagation
 Termination
Lipid Oxidation
 Initiation of Lipid Oxidation
 There must be a catalytic event that causes the initiation of
the oxidative process
 Enzyme catalyzed
 “Auto-oxidation”
 Excited oxygen states (i.e singlet oxygen): 1O2
 Triplet oxygen (ground state) has 2 unpaired electrons in the same spin in
different orbitals.
 Singlet oxygen (excited state) has 2 unpaired electrons of opposite spin in the
same orbital.
 Metal ion induced (iron, copper, etc)
 Light
 Heat
 Free radicals
 Pro-oxidants
 Chlorophyll
 Water activity
 Considerations for Lipid Oxidation
 Which hydrogen will be lost from an unsaturated
fatty acid?
 The longer the chain and the more double
bonds….the lower the energy needed.
 Oleic acid

Radical Damage,
Hydrogen
Abstraction

Formation of a
Peroxyl Radical
 Propagation Reactions
Peroxyl radical
Initiation Ground state oxygen
Hydroperoxide New
Radical

Hydroxyl radical!!
Hydroperoxide Start all over again…
decomposition
 Propagation of Lipid Oxidation

H H H H H H H H
H H H H
R C C C C R R C C C C R
R C C C C R
H H O
H H + Catalyst * + Oxygen
O
 Termination of Lipid Oxidation
 Although radicals can “meet” and terminate propagation
by sharing electrons….
 The presence or addition of antioxidants is the best way in
a food system.
 Antioxidants can donate an electron without becoming a
free radical itself.
 Antioxidants and Lipid Oxidation
 BHT – butylated hydroxytoluene
 BHA – butylated hydroxyanisole
 TBHQ – tertiary butylhydroquinone
 Propyl gallate
 Tocopherol – vitamin E
 NDGA – nordihydroguaiaretic acid
 Carotenoids
 Fats and Oils
Melting and Texture
Think of a fat as a crystal, that when heated will
melt.
 Length of fatty acid chain
 Short chains have low melting points
 Oilsvs soft fats vs hard fats
 Degree of unsaturation
 Unsaturation = presence of double bonds
 Unsaturation = low melting point
 Fats and Oils in Foods
 SOLID FATS are made up of microscopic fat crystals. Many fats
are considered semi-solid, or “plastic”.
 PLASTICITY is a term to describe a fat’s softness or the
temperature range over which it remains a solid.

Even a fat that appears liquid at room temperature contains a small number of
microscopic solid fat crystals suspended in the oil…..and vice versa

 PLASTIC FATS are a 2 phase system:

 Solid phase (the fat crystals)
 Liquid phase (the oil surrounding the crystals).

 Plasticity is a result of the ratio of solid to liquid components.

 Plasticity ratio = volume of crystals / volume of oil
 Measured by a ‘solid fat index’ or amount of solid fat or liquid oil in a lipid

 As the temperature of a plastic fat increases the fat crystals melt

and the fat will soften and eventually turn to a liquid.
Shortening
Plastic range
 Temperature range over which it is solid
(melting point)
 Want a large plastic range for shortening
 Want it to remain a solid at high temps.
 Holding air during baking
Frying Oils
Want a short plastic range
 Liquid or low melting point
 Do not want mono- or diglycerides or oil
will smoke when heated
 Must be stable to oxidation, darkening
 Methyl silicone may be added to help
reduce foaming
Fat and Oil: Further Processing
 Winterizing
 Cooling
a lipid to precipitate solid fat crystals
 DIFFERENT from hydrogenation

 Plasticizing
 Modifying fats by melting (heating) and solidifying
(cooling)
 Tempering
 Holding the fat at a low temperature for several
hours to several days to alter fat crystal properties
(Fat will hold more air, emulsify better, and have
a more consistent melting point)
 Fat Crystals: α, ß’, ß
 The proportion of fat crystals to oil also depends on the melting points
of the crystals.

 Most fats exhibit polymorphism, meaning they can exist in one of

several crystal forms. These crystal forms are 3-D arrangements.
 Three primary crystal forms exist:
 α-form (not very dense, lowest melting point), unstable
 ß’-form (moderate density, moderate melting point), not as stable
 ß-form (most dense, highest melting point), very stable

 Rapid cooling of a heated fat will result in fine α crystals.

 Slow cooling favors formation of the coarse ß crystals.
 Fat crystals are easily observed when butter/shortening is melted and
allowed to re-solidify.
 Fat Crystals in Commercial Oils
α, ß’, ß
 Crystal forms are largely dependent on the fatty acid
composition of the lipid
 Mono-acid lipids (3 of the same fatty acids)
 Mixed lipids or heterogeneous lipids (different FA’s)
 Some fats will only solidify to the ß-form
 Soybean, peanut, corn, olive, coconut, cocoa butter, etc
 Other fats will harden to the ß’-form
 Cottonseed, palm, canola, milk fat, and beef tallow
 ß’ forms are good for baked goods, where a high plastic
range is desired…..but...
 Chocolate Bloom
 In chocolate (cocoa butter), the desired stable
crystal form is the ß-form
 Processing involves conching (blending cocoa
and sugar to a super-fine particle) and
 Tempering (heating/cooling steps).
 Together, these give ß crystals to the final
chocolate
 Fine chocolates control this well.
 Chocolate
Making chocolate
 The polymorphs of chocolate affect quality and keeping quality.
 When making chocolate, the tempering process alters the fat crystals and
transforms to a predominance of ß-forms.
 This process begins with the formation of some ß crystals as “seeds” from
which additional crystals form.
 The chocolate is then heated to just below the temperature for ß-forms to melt
(thus melting all other forms), and allows the remaining fats to crystalize into
ß-forms upon cooling.
Chocolate Bloom
 When chocolate has been heated and cooled, fat and sugar can rise to the
surface, and change crystalline state (fat) or crystallize (sugar).
 When melted fat re-cools, less stable and lower melting point α crystals can
form.
 The different crystals also physically look different (white, grey, etc) against
the brown background of the chocolate bar.