Chapter 1-Introduction

Outline
Food Chemistry ‡ What is Food Chemistry
‡ History of Food Chemistry

Wenjuan Qu ‡ Approach to the Study of Food Chemistry

Jiangsu University
2011 May

What is Food Chemistry History of Food Chemistry

‡ In underdeveloped regions of the world ‡ Carl Wilhelm Scheele (1742-1786)

‡
‡
In developed regions of the world Antoine Laurent Lavoisier (1743-1794)
‡ Food chemistry, a major aspect of food science,
‡ Sir Humphrey Davy (1778-1829)
deals with the composition and properties of food
and the chemical changes during handling, ‡ Justus Von Liebig (1803-1873)
processing, and storage.
‡ Food chemistry is intimately related to chemistry,
biochemistry, physiological chemistry, botany,
zoology, and molecular biology.

Approach to the Study of Food Chemistry Quality and Safety Attributes

‡
‡
Safety is the first requisite of any food
Determining those properties that are important
‡ Quality attributes of food and some alterations during
characteristics of safe, high-quality foods processing and storage
‡ Determining those chemical and biochemical reactions that Attribute Alteration
have important influences on loss of quality and/or Texture Loss of solubility; Loss of water-holding capacity; Toughening;
wholesomeness of foods Softening

‡
Integrating the first two points so that one understands how
the key chemical and biochemical reactions influence quality
and safety
Flavor Development of Rancidity (hydrolytic or oxidative); Cooked or
caramel flavors; Other off-flavors; Desirable flavors
Color Darkening; Bleaching; Development of other off-colors;
Development of desirable colors (e.g., browning of baked goods)

‡ Applying this understanding to various situations encountered Nutritive Loss, degradation or altered bioavailability of proteins, lipids,
value vitamins, minerals
during formulation, processing, and storage of food Safety Generation of toxic substances; Development of substances that
are protective of health; Inactivation of toxic substances
 Chemical and biochemical reactions Chemical and biochemical reactions
‡ Many reactions can alter food quality or safety
Types of reaction Examples
‡ The more important classes of these reactions
Lipid isomerization Cis trans, nonconjugated conjugated
Types of reaction Examples Lipid cyclization Monocyclic fatty acids
Nonenzymic browning Baked goods
Lipid polymerization Foaming during deep fat frying
Enzymic browning Cut fruits
Protein denaturation Egg white coagulation, enzyme inactivation
Oxidation Lipids (off-flavors), vitamin degradation, pigment
decoloration, proteins (loss of nutritive value) Protein cross-linking Loss of nutritive value during alkali
Hydrolysis Lipids, proteins, vitamins, carbohydrates, pigments processing
Metal interactions Complexation (anthocyanins), loss of Magnesium Polysaccharide synthesis In plants postharvest
from chlorophyll, catalysis of oxidation
Glycolytic changes Animal tissue postmortem, plant tissue
postharvest

Effect of reactions on food quality and safety Effect of reactions on food quality and safety

Primary Secondary event Attribute influenced Primary Secondary Attribute

causative event causative event event influenced
Hydrolysis of lipids Free fatty acids react with Texture, flavor, nutritive Heating of green Cell walls and membranes lose, Texture, flavor, color,
protein value vegetables integrity, acids are released, nutritive value
Hydrolysis of Sugars react with proteins Texture, flavor, color, enzymes become inactive
polysaccharides nutritive value Heating of muscle Proteins denature and aggregate, Texture, flavor, color,
Oxidation of lipids Oxidation products react Texture, flavor, color, tissue enzymes become inactive nutritive value
with many other constituents nutritive value, toxic Cis and Trans Enhanced rate of polymerization Excessive foaming
substances can be generated conversions in lipids during deep rat frying during deep fat frying,
Bruising of fruit Cells break, enzymes are Texture, flavor, color, diminished
released, oxygen accessible nutritive value bioavailability of lipids

Analysis of situations encountered during the

storage and processing of food
‡ The variables that are important during the storage and
processing of food Carbohydrates
Product factors Chemical properties of individual constituents;
oxygen content; pH; Water activity; Tg; Wg
Temperature; time; composition of the
Environmental atmosphere; chemical; physical or biological
factors treatments imposed; exposure to light; Wenjuan Qu
contamination; physical abuse Jiangsu University
‡ The variables that are important during the storage and
2011 May
processing of food
 Outline Definition and Classification
‡ Carbohydrates are polyhydroxyl compounds (-OH) that
‡ Definition contain a carbonyl group (-C=O)
‡
‡ Classification
Empirical formula is Cx(H2O)y, especially C2H4O2, C3H6O3
and CH2O, and C5H10O4 and C6H12O5.
‡ Functions ‡ Carbohydrates include two types, based on functional group.
„ Aldoses and ketoses
‡ Carbohydrates include three types, based on single sugar unit.
„ Monosaccharides : 1 unit
„ Oligosaccharides : 2-20 units (Disaccharides: 2 units)
„ Polysaccharides : >20 units

Aldoses Ketoses

Monosaccharides Monosaccharide isomerization

Oligosaccharides Polysaccharides
C1,2 glycosidic bond

cellulose
sucrose C1,4 glycosidic bond

1
amylose
maltose

Aldoses Chiral carbon atom

C2
C4

Glyceraldehyde (1)

C4 epimer for Glucose C2 epimer for Glucose

chiral carbon atom epimer Glucose (4)

Enantiomers D/L enantiomers

‡ Enantiomers are stereoisomers that are complete
mirror images of each other, much as one's left and
right hands are "the same" but opposite.
‡ Only the D-isomer is found in living organisms.

L-glyceraldehyde D-glyceraldehyde D-glucose L-glucose

 Ketoses Chain and ring types

C
C5 β

α anomer—opposite side
C5 epimer for Fructose
β anomer—same side

/ anomer Drawing
1
2 β
6
3 5 2
4 4 3
1 α
5

Pyranose ring Furanose ring

Pyranose ring is more stable than furanose ring

Configuration and conformation Functions

‡ Configurations are the permanent geometry that ‡ Carbohydrates provide necessary caloric intake and
results from the spatial arrangement of its bonds. nutrition.
‡ Conformations are the arrangement of the parts of an
‡ Carbohydrates are widely used as important
object.
sweeteners and preservers.
„ Two polymers which have the same chemical
composition but can only be made identical by ‡ Carbohydrates provide favorite colors and flavors.
breaking and reforming bonds are said to be two ‡ Carbohydrates have good viscosity, gelatinization
configurations of that polymer (e.g. L/D, α/β). and stabilization.
„ Two polymers which differ only by rotations about
single bonds are said to be two different
conformations of that polymer (e.g. chair/boat
form).
 Outline
‡ Definition
Lipids
‡ Classification
‡ Functions and roles
Wenjuan Qu ‡ Physical properties
‡
Jiangsu University
Chemical reactions
2011 May
‡ Quality analyses

Lipids Fatty acids

‡ Definition: Any of a group of substances that in ‡ Structure
general are soluble in organic solvents, but are not
soluble in water. Mostly made up of C, H and O, (Water-soluble tail)
Some P, N and S.
Polar end - Hydrophilic end
‡ Classification
„ Fatty acids
„ Glycerol
„ Phospholipid (Fat-soluble tail)
„ Waxes Non-polar end - Hydrophobic end
„ Sterols

Saturated and Unsaturated Saturated and Unsaturated

fatty acids fatty acids
‡ Saturated fatty acids
„ Saturated fatty acids do not contain any double bonds or
other functional groups along the chain.
„ Saturated fatty acids are straight chains
‡ Unsaturated fatty acids
„ Monounsaturated fatty acids
‡ Monounsaturated fatty acids have one double bond

‡ Monounsaturated fatty acids are widespread in the

living world where they occur mostly as the cis-isomer.
„ Polyunsaturated fatty acids
‡ Polyunsaturated fatty acids have two or more double
bonds, especially conjugated fatty acids
Cis and Trans fatty acids Nomenclature
‡ Two different ways to make clear where the double bonds are
located in molecules:
„ Cis/trans-Δ : The double bond is located on the xth
x

carbon-carbon bond, counting from the carboxyl

terminus. The cis or trans notation indicates whether the
molecule is arranged in a cis or trans conformation. In the
case of a molecule having more than one double bond, the
9 12 9,12
notation is, for example, cis-Δ , cis-Δ or cis-Δ .
„ ω-x : A double bond is located on the x carbon-carbon
th

bond, counting from the ω, methyl end of the chain.

Sometimes, the symbol ω is substituted with a lowercase
letter n, making it n-9/ω-9, n-6/ω-6 or n-3/ω-3.

Numbering Acylglycerols

Monoacylglycerol Diacylglycerol

‡ Fatty acids can be represented by a simply numerical

expression consisting of two terms separated by a colon.
‡ * Essential fatty acids (EFA): ω-3 and ω-6 fatty acids
can’t be constructed within human or animals from other Triacylglycerol
components and therefore must be obtained from the diet.

Triacylglycerols (TAG) Acylglycerols

‡ Glycerol esters of fatty acids make up to 99% of the liquid
of animal and plant origin, have been traditionally called
fats and oils. This distinction is based on whether the
material is solid or liquid at room temperature.
‡ Classification
„ Milk fats
Glycerol Fatty acids TAG „ Lauric acids
„ Vegetable butters
„ Animal fats
„ Oleic-linoleic acids
„ Linolenic acids
„ Marine oils
Nomenclature Phospholipids
‡ The sn system is applicable to both synthetic and natural ‡ phospholipids are used for any lipid containing
fats. sn-1 is R1，sn-2 is R2 and sn-3 is R3 (top-to-bottom)
phosphoric acid as a mono- or diester.
sn-1 ‡
sn-2
sn-3
1-stearoyl-2-oleoyl-3-myristoyl-sn-glycerol
sn-glycerol-1-stearate-2-oleate-3-myristate
sn-18:0-18:1-16:0
sn: used immediately preceding the term
“glycerol”, indicates that the sn-1, sn-2, and sn-3 phosphoric acid
positions are listed in that order

Waxes Sterols
‡ Fatty acid + Long chain alcohol ‡ Male & female sex hormones
‡ Important in fruits: ‡ Bile acids
„ Natural protective layer in fruits, vegetables, etc. ‡ Adrenal corticosteroids

„ Added in some cases for appearance and ‡ Cholesterol

protection.

Beeswax Spermaceti
(myricyl palmitate) (cetyl palmitate)

Lipid properties Physical properties

‡ Physical properties ‡ MPconjugated double bond > MPnon-conjugated
„ Melting point (MP) (40-55 C)
o
double bond
‡ Long chain fatty acids pack better than short chain ones ‡ MP has relationship with digestibility.

ƒ MPlong > MPshort ‡ MP ＜37 C, digestibility = 97.98%; MP 37 C-50 C,

o o o

‡ Saturated fatty acids pack better than unsaturated ones

o
digestibility = 90%; ＞50 C, indigestible.
ƒ MPsat. > MPunsat. „
o
Boiling point (BP) (180-200 C)
ƒ Hydrogenation increase the MP. ‡ BP increases with increased carbon chain of fatty acids

‡ Trans fatty acids pack better than cis ones ‡ Saturated fatty acids and unsaturated ones have similar

ƒ MPtrans. > MPcis. BP.

„ Density < Density
fat water
Chemical properties Hydrolysis
‡ Lipolysis ‡ Types of hydrolysis
„ Saponification (base catalyzed)
„ Acid hydrolysis

‡ Hydrogenation „ Enzymatic hydrolysis (lipase catalyzed)

„ Interesterification
‡ Hydrolysis products

‡ Autoxidation „ Small quantities of free fatty acids

‡ Interesterification ‡ Contribute flavors to cheese, milk, chocolate

‡ Cause off-flavors in milks, fruits and vegetables

Interesterification Interesterification
‡ Interesterification-Rearrange fatty acids so they ‡ Basic catalyst such as NaOH、KOH、NaOCH3、
become distributed randomly among triglycerol organic base
molecules of fat ‡ Mechanism：

Interesterification Hydrogen
‡
‡ Acid catalyst such as sulfuric acid and sulfonic acid Addition of hydrogen across double bonds
‡ Produces triglycerides with higher melting points
Mechanism：
‡ Liquid fats convert to semi-solid fats or soft fats convert
into firmer fat
‡ Improves oxidative stability
‡ Produces Trans fats
 Trans fatty acids
‡ Refer to triglycerides containing unsaturated fatty acids in
trans conformation.
‡ Found in partially hydrogenated fats or oils
‡ Health problems
„ Increase cardiovascular disease. Eating just 5 grams of it
per day increases the risk of heart disease 25 %.
„ Increase risks of other chronic diseases, such as cancer,
obesity, and diabetes.
‡ FDA adopted new food labeling
„ Label gives weight of trans fat.
„ The regulation allows trans fat levels of less than 0.5
grams per serving to be labeled as 0 grams per serving.

Lipid autoxidation Lipid autoxidation

‡
‡
Effects of lipid autoxidation
Lipid autoxidation - free radical reactions.
„ Flavor quality loss
‡ Initiation, Propagation and Termination
‡ Rancid flavor

‡ Changes of color and texture

‡ Consumer acceptance

„ Nutritional quality loss

‡ Essential fatty acids

‡ Vitamins

„ Health risks
‡ Growth retardation

‡ Heart diseases

‡ Producing free radicals

Initiation Initiation mechanisms

‡ Initiation of autoxidation occurs when hydrogen atom at -
methylene group in double bonds of unsaturated fatty
acids is removed to form an alkyl radical (R·)
‡
Initial generation of free radicals is slow
„ Initiated by singlet oxygen (1O2)
‡ Metastable, excited energy state of O2
‡ Two unpaired electrons in same orbital
‡ Oxygen raised to excited state by light.
„ Inactive by blanching (short energy –potooxidation)
„ Promoted by pigments (sensitizers)
‡ e.g. chlorophyll, riboflavin
‡ Oxygen raised to excited state by enzymes –lipoxygenase
‡ Inactivate by blanching (heating to denature enzymes)
‡ Oxygen raised to excited state by metal ions (e.g. Fe, Co,
Cu)
„ Naturally in food or from metal equipment
„ Using chelating agents (e.g. EDTA) to prevent
oxidation.
 Hydroperoxide formation Hydroperoxide decomposition

Autoxidation mechanism Oxidation mechanism

Initiation
Propagation

Bad way Good way

Factors influencing lipid oxidation

Oxidation mechanism rate
‡ Fatty acid composition
„ number, position and geometry of double bonds affect
Termination
the oxidation rate.
„ Saturated triglycerides are stable at room temperature
„ Unsaturated fatty acids are promotions of lipid oxidation
Hydroperoxide „ Relative oxidation rates : Arachidonic : linolenic: linoleic
decomposition : oleic= 40:20:10:1
„ Conjugated double bonds are more reactive than non-
conjugated ones.
„ Cis configuration is more reactive than trans one.
‡ Free fatty acid percent
„ Free fatty acids react faster than triglycerides.
Factors influencing lipid oxidation Factors promoting or suppressing
rate lipid oxidation rate
‡ Oxygen concentration:
„ At low oxygen pressure, oxygen pressure is positive to
oxidation rate
„ Under enough oxygen supply, oxygen pressure has no effect
‡ Temperature
„ Oxidation rates increase with increased temperatures
‡ specific surface area
„ Oxygen rate is positive to specific surface area
‡ Water activity
„ Oxidation rate is high at aw < 0.1, such as rancidity in
dehydrate foods
„ Metal ions (e.g. Fe, Co, Cu)

Singlet Oxygen Quenching of

Antioxidant enzymes Tocopherols

Metal Ions – EDTA Antioxidant mechanism

Synthetic antioxidants Natural antioxidants
‡ Vitamin C
‡ Tocopherol
‡ Quercetin
‡ Anthocyanin
‡ Radical scavenging antioxidants break free radical
chain reaction by donating hydrogen to free
radicals

Lipid quality analyses Acid Value (AV)

‡ Acid value ‡ Definition: Number of mg of KOH required to
‡ Saponification value neutralize the Free Fatty Acids (FFA) in 1 g of fat.
‡ Iodine value ‡ Acid vale (AV) expresses the number of free fatty
‡ Peroxide value acid (FFA) in oil.
‡ Ester value
9 Constant values express the characteristics of oil
composition
g fat
e.g. iodine value, saponification value
9 Variable values express the changes in oil property
e.g. acid value, peroxide value

Saponification Value (SV) Saponification Value

‡ Saponification - Hydrolysis of ester (Tri-acylglycerol, ‡ SV expresses the oil characteristics and molecular weight
TAG) under alkaline condition. of TAG.
‡ Definition : Number of mg of KOH required to saponify 1 „ Higher SV means lower molecular weight of TAG.
g of fat „ For fat and oil, the SV is normally around 200.

FFA (%) =AV/SV×100%

Ester value (EV) Iodine Value (IV)
‡
‡ Definition : Number of mg of KOH required to saponify Definition: Number of iodine (g) absorbed by 100 g of oil.
glyceride in 1 g of fat. „ 1 g of fat adsorbed 1.5 g of iodine, iodine value is ?

Iodine Value =

Number of Double Bonds per

Molecule Iodine Value

‡ Molecular weight and iodine value can calculate

the number of double bonds.
‡ The unknown compound has molecular weight of
878 and iodine value of 173. Determine the
number of double bonds in the unknown compound.

Peroxide Value (POV) Peroxide Value

‡ Definition: Number of ml of standard Na2S2O3
required to titrate 1 g of fat or express by iodine
content (%).
‡ Peroxide value (POV) expresses the degree of
oxidation in the initial period.
 Amino acids
‡ The α-carbon is the carbon to which a functional group is
attached.
Amino acid, peptide & protein

Wenjuan Qu
Jiangsu University
2011 May

Groups of amino acids Aliphatic amino acids

‡ Amino acids can be classified into several categories based
on the side chains：
„ Aliphatic amino acids
„ Aromatic amino acids
„ Hydroxy amino acids
„ Acidic amino acids
„ Basic amino acids
„ Amide amino acids
„ Sulfur-containing amino acids
„ Secondary amino acids

Aromatic amino acids Hydroxy amino acids

Acidic amino acids Amide amino acids

‡ The side chains contain a carboxyl group

‡ Negatively charged (acid) at neutral pH
‡ Carboxyl groups function as nucleophiles in some enzymatic
reactions

Basic amino acids Sulfur-containing amino acids

‡ Hydrophillic 亲水的 nitrogenous bases

‡ Positively charged (basic) at neutral pH

Secondary amino acids Groups of amino acids

‡ Amino acids can be classified into several categories based on
the degree of interaction of the side chains with water:
„ Hydrophobic amino acids: Phe, Leu, Ile, Val, Ala, Met,
Pro, Trp, Tyr.
„ Polar and uncharged amino acids: Ser, Thr, Gly, Asn, Cys
„ Positively charged amino acids: Lys, Arg, His.
„ Negatively charged amino acids: Asp, Glu.
Chemical properties pI 等电点

pI 等电点 pI 等电点
‡ For amino acids with more than two ionizable groups, such as
lysine 赖氨酸 for example, the same formula is used, but
this time the two pKa's used are those of the two groups that
lose and gain a charge from the neutral form of the amino
acid.

General philosophy
‡ Definition: The term flavor has evolved to a usage
that implies an overall integrated perception of all of
Flavors the contributing senses (smell, taste, sight, feeling,
and sound) at the time of food consumption.
‡ Classification
Wenjuan Qu
„ Smell-odors and flavors
Jiangsu University
„ Taste
2011 May
„ Nonchemical senses-sight, sound, and feeling
Methods for flavor analysis Sensory assessment of flavors
‡ Isolation technique ‡ Formal panels
‡ Distillation technique ‡ Determination of detection thresholds

‡ Fused-silica capillary column technique ‡ Odor units (OU)

‡ GC-MS technique ‡ Aroma extract dilution analysis (AEDA)

‡ HPLC technique ‡ Characterizing or character-impact compounds

Taste and nonspecific saporous

sensations Vegetables, fruit, and spice flavors
‡ Taste substance: sweet, bitter, sour, and salty ‡ Sulfur-containing volatiles
„ Sweet modality ‡ Unique sulfur compound in Shiitake muchrooms
„ Bitter taste modality ‡ Methoxy alkyl pyrazine volatiles
„ Salty and sour taste modalities ‡ Enzymically derived volatiles
‡ Flavor enhancers ‡ Volatiles from branched-chain amino acids
‡ Astringency ‡ Flavors derived from the Shikimic acid pathway
‡ Pungency ‡ Volatile terpenoids in flavors
‡ Cooling ‡ Citrus flavors
‡ Flavors of herbs and spices

Flavors development
‡ Flavors from lactic acid-ethanol fermentation
‡ Flavor volatiles from fats and oils
‡ Flavor volatiles in muscle foods and milk
‡ Volatiles in fish and seafood flavors
‡ Development of process of reaction flavor volatiles
„ Thermally induced process flavors
„ Volatiles derived from oxidative cleavage of
carotenoids
 Outline
z Chemistry and nutrition of vitamins
Vitamins z Water-soluble vitamins

u U n i v e r s i t y z
z Fat-soluble vitamins
General causes for of vitamin loss in food
z Variation in vitamin content

J i a n g s Food chemistry
Qu Wenjuan

2010 September
z
z
z
z
z
Postharvest changes in vitamin content of foods
Preliminary treatments: trimming, washing, milling
Effects of blanching and thermal processing
Losses of vitamins following processing
Influence of processing chemicals and other food
components

1 2

Vitamins Fat-soluble vitamins

z A diverse group of organic compounds that are z Classification
nutritionally essential micronutrients z

y
Vitamin A, Vitamin D, Vitamin E, Vitamin K
z

z
and diseases

s u i v s i t
necessary for growth, vitality, health, general well being,

e r
and for the prevention and cure of many health problems

U n
z

z
Structure and general properties

ng
Functions in vivo Stability and modes of degradation

Jia
z Coenzymes or their precursors z Bioavailability
z Components of the antioxidative defense system
Vc, Carotenoids, VE z Analytical methods
z Factors involved in genetic regulation
z Speciallied functions
VA in visions, ascorbic acids in hydroxylation reactions

3 4

Vitamin A (Retinol) Carotenoids

z also called retinol
z Carotenoids contribute significant vitamin A activity to
z Unsaturated hydrocarbons, found in trans form naturally
z A basic structural unit of the molecule a five-carbon isoprene segment
foods

u U n i v e r s i t y
z All trans isomers have the greatest vitamin A activity z Of ~600 carotenoids, ~50 have some provitamin A
activity which partially converted to vitamin A in vivo.
Naturally in trans form.
β-carotene exhibits the gratest pro-vitamin A activity.

J
H3C

i a n g sCH3

CH3
CH3 CH3

Retinol
OH
z

z
About 50% of the vitamin A activity.
Singlet oxygen (1O2) scavenger

5 6

1
 β - Carotene and Retinol Benefits of Vitamin A
CH 3
CH 3 CH 3 CH 3
H3 C
Provitamin A

i t y
CH 3

s
CH 3 CH 3 CH 3
DEFICIENCY SYMPTOMS:

e r
CH 3
May result in night blindness;

i a n g s u U n i v H3 C CH 3
CH 3
Oxidation

CH 3 O
C H
increased susceptibility to
infections; rough, dry, scaly
skin; loss of smell & appetite;
frequents fatigue; lack of

J
tearing; defective teeth &
CH 3 Retainal gums' retarded growth.
- 2H

CH 3 CH 3
H3 C CH 3
CH 2 OH Vitamin A excess, also called hypervitaminosis A, is a toxic condition produced by
a high intake of vitamin A, generally 150,000 μg daily over a period of several
CH 3 Retinol (Vitamin A) months.

7 8

Sources of Vitamin A and beta-carotene Stability of Vitamin A and β-carotene

z Geometric isomerization
z

y
Target: the unsaturated chain

s u U n i v e r s i t z
z
z
trans cis
Heat or light can induce isomerization
Oxidation

Jia ng z Belong to lipids, so lipid oxidation also happens to

both

9 10

Vitamin D Benefits of Vitamin D

z Although about 10 compounds

most important ones are

U n i v e r
ergocalciferol (vitamin D2) and

u s
have vitamin D activity, the two

i t y
g s
cholecalciferol (vitamin D3).
z

J i a n
Vitamin D3 represents the
dietary source, while vitamin
D2 occurs in yeasts and fungi.

Vitamin D3
DEFICIENCY SYMPTOMS: May lead to rickets, tooth decay, softening of
bones, improper healing of fractures, lack of vigor, muscular weakness,
inadequate absorption of calcium, retention of phosphorous in the kidneys

11 12

2
 Sources of Vitamin D Vitamin E (Tocopherols)
R1
HO

y
CH3 CH3 CH3

t
CH3

e r s i
R2 O CH3

i v
R3

J i a n g s u U n Trivial Name

α-Tocopherol
β-Tocopherol
γ-Tocopherol
σ-Tocopherol
Chemical Name

5,7,8-Trimethyltocol
5,8-Dimethyltocol
7,8-Dimethyltocol
8-Methyltocol
R1

CH3
CH3
H
H
R2

CH3
H
CH3
H
R3

CH3
CH3
CH3
CH3

13 14

Benefits of Vitamin E Source of Vitamin E

u U n i v e r s i t y
Jia ng s
15 16

Oxidation of Vitamin E Resonance of α- Tocopherol Radicals

CH3

z
α-Tocopherol
HO
Good stability in the absence of oxygen and CH3 CH3 CH3 CH3

t y
oxidizing lipids

i
H3C O

r s
CH3

v e
Stable to heat R•, RO •, or ROO •

i
RH , ROH , ROOH

n
CH3

U
CH3
•
As antioxidants

u
O

s
O

g
CH3

n
CH3
Scavenge free radical, e.g. 1O2, . OH, ROO . ROO-

i a
H3C O C16H33 +

J
H3C + O C16H33

z
CH3
Hydrogen donating ability : CH3

δ > γ > β > α - Tocopherol R•, RO •, or ROO • H2O

CH3 OH C H
16 33
CH3
O
CH3 CH3 O

•
O CH3
H3C O

α-Tocopherylquinone
H3C O C16H33
CH3 OH
H 3C O C16H33 CH3
CH3

17 18

3
 Regeneration by Vitamin C Vitamin K
z Vitamin K1, or phylloquinone, is synthesized by plants;
the members of the vitamin K2 are of microbial origin.
z

t y
Photochemical degradation

s u U n i v e r s i
J i a n g
19 20

Benefits of Vitamin K Sources of Vitamin K

u U n i v e r s i t y
Jia ng s Vitamin K deficiency is seldom naturally encountered in higher
animals because the vitamin is usually adequately supplied in the
diet, besides being synthesized by intestinal bacteria.

21 22

Water-soluble vitamins Ascorbic Acid

z
z
A carbohydrate-like compound
Vitamin C (ascorbic acid)
z Acidic and reducing properties ----contributed by 2,3-
z B vitamins
z

u U n i v e r s i t y
thiamin (vitamin B1), riboflavin (vitamin B2), vitamin
B6, niacin (nicotinic acid, vitamin B3), vitamin B12,
z
z
enediol moiety
Highly polar
pKa1=4.04 @ 25 oC , ionization of the C3 hydroxyl group

s
folic acid, pantothenic acid, and biotin.

J i a n g 2,3-enediol

L-ascorbic acid

23 24

4
 Benefits of Vitamin C Sources of Vitamin C

u U n i v e r s i t y
J i a n g s
DEFICIENCY SYMPTOMS: May lead to soft & bleeding gums, swollen or painful
joints, slow-healing wounds & fractures, bruising, nosebleeds, tooth decay, loss
of appetite, muscular weakness, skin hemorrhages, capillary weakness, anemia,
impaired digestion.

25 26

Oxidation of L-ascorbic acid Oxidation of L-ascorbic acid

• L-dehydroascorbic acid loses reducing power

z
•All have vitamin C activity except 2,3-diketogulonic acid because they are almost
completely reduced to L-ascorbic acid in body Highly susceptible to oxygen
z

t y
Catalytic effects of metal ions (Cu2+, Fe3+)

s u U n i v e r s i z
z
Heat and light accelerate the oxidation process
Neutral or alkaline condition favors oxidation of L-
ascorbic acid

Jia
AA

ng
Two electrons oxidation
and hydrogen dissociation

Vitamin C Activity
DHAA
Loss of
reducing power
Neutral or
alkaline pH

Maillard reaction
DKG No vitamin

Brown
pigments
activity

27 28

L-ascorbic acid as antioxidants Thiamin

z Mechanism: its availability for energetically z Primidine + methylene + thiazole

t y
favourable oxidation.
z

s u U n i v e r s i
Reactive oxygen species oxidize (take electrons
from) ascorbate first to monodehydroascorbate pyrimidine thiazole

g
and then dehydroascorbate. H3C N NH 2 S CH 2CH 2OH

J i a n
The reactive oxygen species are reduced to
water while the oxidized forms of ascorbate are
relatively stable and unreactive.
N
CH 2

Methylene
bridge
N
CH 3

29 30

5
 Benefits of Thiamin Sources of Thiamin

u U n i v e r s i t y
J i a n g s
DEFICIENCY SYMPTOMS: Systemic thiamine deficiency can lead to myriad
problems including neurodegeneration, wasting and death.
Thiamine is found naturally in the following foods, each of which contains at least 0.1
mg of the vitamin per 28-100 g: Green peas, Spinach, Liver, Beef, Pork, Nuts, Pinto
beans, Bananas, Soybeans, Goji berries, Whole-grain and Enriched Cereals, Breads,
Yeast ,the aleurone layer of unpolished rice, and Legumes.

31 32

Degradation of Thiamin Riboflavin (Vitamin B2)

z All derivatives of riboflavin are given the name flavins
z pH z The flavin derivatives FAD and FMN are synthesised from dietary
riboflavin (vitamin B2) and ATP. They function as coenzymes in a

y
z

t
Neutral or greater pH values favor its degradation

i
large of flavin-dependent enzymes in oxidation-reduction reactions
z

r s
in bodies.

e
Sulfiting agent (SO3-2)
z ,US

U n i v
federal regulation prohibits the use of sulfiting

ng s u
agents in foods that are significant sources for thiamin adenine

Jia
z Water activity
z Stable at low water activity
z Sensitivity to heat is depending on water activity
and pH ribose
Riboflavin Flavin mononucleotide Flavin adenine dinucleotide
(FMN) (FAD)

33 34

Oxidation-reduction behavior of flavins Benefits of Riboflavin

t y
2e-, 2H+

s u U n i v e r s i
n g
Oxidized form

a
Reduced form

J i
Bright yellow

FAD
In physiological condition, FAD/FADH2
involve in electron-transfer reaction
Colorless

FADH2

DEFICIENCY SYMPTOMS: sore throat, swelling of mucous membranes,

mouth or lip sores, anemia, and skin disorders.

35 36

6
 Sources of Riboflavin Niacin (Vitamin B3)
z Niacin is the generic term for nicotinic acid and derivatives.
z The most stable of vitamins
z Not affected by light, no thermal loss of vitamin acitivity during food processing

y
z Heat converts nicotinamide to nicotinic acid, both have vitamin B3 activity

i t
z

s
Coenzyme forms of Niacin

e r
z

v
NAD, NADP---in many dehydrogenase reactions.

J i a n g s u U n i Nicotinic acid
Nicotinamide adenine
dinucleotide (NAD)

Nicotinamide adenine
dinucleotide
Nicotinamide phosphate (NADP)

37 38

Benefits of Niacin Sources of Niacin

u U n i v e r s i t y
Jia ng s
DEFICIENCY SYMPTOMS: cracked and red lips, inflammation of the lining of
mouth and tongue, mouth ulcers, cracks at the corners of the mouth (angular
cheilitis), and a sore throat. A deficiency may also cause dry and scaling skin, fluid
in the mucous membranes, and iron-deficiency anemia. The eyes may also become
bloodshot, itchy, watery and sensitive to bright light.

39 40

Vitamin B6 Benefits of Vitamin B6

z A group of compounds having the vitamin activity of prodoxine
z A cofactor in many reactions of amino acid metabolism, including
transamination, deamination, and decarboxylation.
z

t y
Necessary for the enzymatic reaction governing the release of glucose from

s i
glycogen.

n g s u U n i v e r
J i a z
z
z
Light-induced degradation
Thermal degradation
Thermal interconversion The classic clinical syndrome for B6 deficiency is a seborrheic dermatitis-like
eruption, atrophic glossitis with ulceration, angular cheilitis, conjunctivitis,
intertrigo, and neurologic symptoms of somnolence, confusion, and
neuropathy

41 42

7
 Sources of Vitamin B6 Folate (Vitamin B9)
z A group of compounds having chemical structure and nutritional
activity similar to folic acid
z Stabilility denpending on food systems. Complicated

u U n i v e r s i t y environmental factors (catalysts, oxidants, pH, buffer ions, etc. )

J i a n g s
43 44

Benefits of Folate (Vitamin B9) Sources of Folate

u U n i v e r s i t y
Jia ng s
Folic acid deficiency may cause poor growth, gray hair,
swollen tongue (glossitis), mouth ulcers, peptic ulcer, and
diarrhea. It may also lead to certain types of anemias.

45 46

General Causes of Losses in Food Vitamins-Losses during processing

z Postharverst changes in vitamin content of foods
Vitamin Fresh cooked blanching Blanching & retort
z

y
Enzymes contribute to changes of vitamin content
z

U n
Water-soluble vitamins
z Leaching

s u r s i t
Preliminary treatments: trimming, washing, milling
z

i v e
Discarding stem, skin, or others
Ascorbic
acid
19 33 53

z
z
z

J i a n g
Effects of blanching and thermal processing
Vc, Thiamin, Niacin, etc
Losses of vitamin during storage after processing
Influence of processing chemicals and other food
components
z Hypochlorous acid (HOCl), hypochlorite anion (OCl-), Cl2, SO2,
Nitrite, etc
Thiamin

Niacin

%
7

7
5

10
48

30

47 48

8
 Food Pyramid

u U n i v e r s i t y
J i a n g s
49

u U n i v e r s i t y
Jia ng s

u U n i v e r s i t y
J i a n g s