Professional Documents
Culture Documents
JAN 23
FOOD CHEMISTRY
- post harvest handling of fresh produce
- food formulation
- food processing
- storage
- proper investigation/research: facts derived from the study of one food or model system
Examples:
1. EFFECT OF FOOD ADDITIVE:
- antioxidant in preventing rancidity: stability of sweetened-dried young coconut meat with tocopherol
randomly selected from 1 batch will enhance our understanding of the stability of the rest of the
products and of the future products.
- synthetic sweetener as substitute for sugar in polvoron: 60% substitution of sugar significantly
reduced calories of the product without affecting sweetness (perceived). Results can be used in
modifying similar products or other products.
2. POST-HARVEST CHANGES IN FRUITS
- biochemical/chemical changes (ripening) in saba banana at 15C; results will enhance our
- biochemical/chemical changes in solo papaya under MA (Modified Atmosphere) storage
> quality-sensory and nutritive value: influenced by composition and properties of components
> sensory attributes color, aroma, flavor, taste, texture
> chemical and biological reactions: desirable or undesirable
Desirable enhance quality of food; e.g. tenderization of meat during aging
Undesirable deterioration of food; biochemical/chemical reactions resulting to loss of quality
attributes specific to the food.
Reactions Results
MECHANICAL DAMAGE
- physical changes which may induce biochemical/chemical reactions
Examples:
1. Bruising of fruits, vegetables, root crops
1
2. Heating
3. Low temperature, refrigeration, freezing
2. Heating
- cause protein denaturation: change in texture, flavor, etc.
PRESERVATION OF FOODS
A. Short term preservation extend freshness of fruits, vegetables, seafoods, beef, pork, chicken
(poultry), etc.
- refrigeration, modified atmosphere packaging (MAP), controlled atmospheric packaging (CAP)
B. Long term preservation canning, drying, freezing
In the selection of the method consider the following: compostion, components of food, post harvest, post
mortem biochemical/chemical changes in food (may occur immediately after harvest/death, during
processing or storage, thus there is a need to study components of food, macro components, and micro
components).
Color of food:
1. Pigments inherent in food* - fresh produce
2. Colorants (added) processed foods
*preserved during processing/preparation?
PIGMENTS
- normal constituents of cells or tissues of plants or animals that impart color
- in fruits, leaves, other parts of plants, animal tissues, blood, fish, shellfish, other seafoods
- in harvested fruits/vegetables and muscle foods, pigments also include compounds/substances
formed on heating, storage or processing
- also synthesized by some microorganisms
JAN 30
COLORANT
- general term which refers to any chemical compound that imparts color
- food additives, i.e., intentionally added
- can be a natural pigment extracted or prepared (e.g. annatto, turmeric, carotenoids, anthocyanins)
from a plant source or it can be synthetic
- regulated particularly the synthetic food colors (subjected to toxicological tests prior approval to use)
CHLOROPHYLL
- belong to the group of tetrapyrrole compounds
- all classes of photosynthesized porphyrin pigments
- green pigments involved in the photosynthesis of higher plants
TYPES
1. Chlorophyll a in all plants, algae and cyanobacteria
2. Chlorophyll b in plants and green algae only
3. Chlorophyll c in photosynthesis chromista and dinoflagellates
4. Chlorophyll d in red algae together with type a
STRUCTURE:
- porphyrin ring with 4 pyrrole group and Mg
a Mg chelated tetrapyrrole structure with methyl substituents; with phytol** group esterified to
propionate at the C-7 position
**phytol a 20C monosaturated isoprenoid alcohol
Type R group*
**STRUCTURE
- Location:
Chloroplasts plastid bodies where chlorophylls are located
Grana smaller particles with in chloroplasts composed of lamellae where chlorophyll molecules are
embedded
Stroma between grana
- Occurrence in plants associated with lipids, proteins and lipoproteins bound to these molecules
How?
Held together in a monolayer by:
- mutual attraction
- affinity of phytol tail for lipids
- affinity of the hydrophobic planar porphyrin ring for proteins
3
- Properties: Physical and Chemical
Physical, solubility in various solvents:
S Soluble
I Insoluble
SltS Slightly soluble
AlmI Almost Insoluble
pheophytin a S S S S SltS I
chlorophyll b S S S S AlmI I
pheophytin b S S S S AlmI I
Chlorophyllide S
a/b* *In General Insoluble in Oil
pheophorbide S
a/b
Chemical Properties
- chemical changes in structure of chlorophyll
- alterations in the structure are manifested through changes in color of disappearance of color
Chemical changes
1. Isomerization of chlorophyll by inversion of carbomethoxy group at C10
- may occur during heating in the presence of organic solvent
Ex.
chlorophyll a chlorophyll a
These isomers have stronger A on C18
chlorophyll b chlorophyll b
Reverse phase HPLC column
*observed in spinach leaves when heated at 100C for 10 min, 5-10% conversion
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2. Pheophytinization removal of Mg++ and its replacement with 2H+
-Mg++, +2H+
chlorophyll pheophytin
bright green dull olive brown
compare susceptibility of chlorophyll a with chlorophyll b to pheophytinization
- chlorophyll a is more susceptible; chlorophyll b is more stable
-phytol
pheophytin pheophorbide
olive brown olive brown
-Mg++, +2H+
chlorophyllide pheophorbide
bright green olive brown
6. Formation of pyropheophytin
-CO2CH3* at C10, +H at C10
pheophytin pyropheophytin
*CO2CH3 carbomethoxy
7. Formation of pyropheophorbide
-Mg++, +2H+
chlorophyll pheophytin
(bright green) (olive brown)
-Mg++, +2H+
chlorophyllide pheophorbide
(bright green) (olive brown)
pyropheophytin
CO2CH3* at C10,
+H at C10
pyropheophorbide
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FEB 02
CHLOROPHYLLASE an esterase; cleavage of phytol from chlorophyll and pheophytin (derivative of
chlorophyll)
In fresh leaves, chlorophyllide is formed only when chlorophyllase is heat activated during post harvest
e.g. during blanching
- increase in +charge on the 4 pyrrole Ns reduces the equilibrium constants for the formation of the
reaction intermediate
pH of the tissue
pH 9.0 very stable during heating
pH 7.0 unstable during heating
6
Q.1. What is the pH of green leafy vegetables, green beans and other green vegetables?
A. Most leafy vegetables have pH >3.0, hence may remain stable during cooking/processing
Q.2. Why is it that many green leafy vegetables loss their bright green color on cooking, particularly
with longer cooking period?
A. There are factors that influence effect of heating which include pH and cooking. Cooking
(long exposure to heat)/processing destroys structure of cells, cell walls, membranes, etc.,
which can result to: 1) release of acids (inherent) and; 2) formation/production of acid.
Example: spinach, peas, green beans observed to release/produce 10 acids.
Acids implicated:
1. Acetic
2. Pyrrolidone carboxylic acid (major cause)
3. Oxalic acid
4. Malic acid
5. Citric acid
6. Succinic acid
7. Fatty acids from fat hydrolysis
8. Other acids
Detergents
- cationic detergents (+) repel H+ at the membrane surface
- limit H+ diffusion into the cell
2. EXPOSURE TO LIGHT
- cause photodegradation of chlorophyll* : loss of desirable green color
*occurs:
1. during senescence
2. during storage
3. when extracted
4. when there is cell damage, e.g. during processing
Healthy plant cells chlorophyll is protected from destruction by light due to the presence of
surrounding carotenoids and other lipids
7
SUGGESTED MECHANISM OF PHOTODEGRADATION
opens* fragments
tetrapyrrole lower mol. wt. compounds
Singlet oxygen and hydroxyl radicals can react with other tetrapyrrole chlorophyll or other porphyrin
to form peroxides and more free radicals -> total loss of color
lipoxygenase
lipids free radicals
4. IRRADIATION: GAMMA-IRRADIATION
Fruits/vegetables before storage
irradiation
chlorophyll pheophytin
5. FERMENTATION
Decrease in pH due to acid formed aside from the inherent acids present
fermentation
chlorophyll pheophytin, chlorophyllide,
normal pH pheophorbide, acidic conditions, lower than normal pH
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FEB 06
6. ADDED INGREDIENTS: ACID, LIME
Acid pH, reduction
- pheophytinization
Q. Why?
H+ ions from added acid can replace Mg++ in the porphyrin ring (Note: 2H+/Mg++
Questions:
1. Can we remove H+ and add back Mg++?
2. Can another metal ion replace H+?
DEGRADATION
- mechanisms/reactions of degradation
- causes, factors which influence (flavor) degradation
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- alkaline salts:
a. Ca + NaH2PO4
b. MgCO3 in combination with Na3PO4
c. Na2CO3
d. Ca(OH)2 + Mg(OH)2
e. Ethyl cellulose + 5% Mg(OH)2 as interior coating of cans
- a and b are not highly recommended due to softening of tissue and alkaline flavor
- d [Ca(OH)2 + Mg(OH)2]
known as Blair Process, originally used to preserve texture and crispness of some vegetables
not very successfully commercially for the retention of the desirable green color due loss of color in
less than 2-month storage. Why? Salts were not effective in neutralizing acid in the inner tissues of
vegetables at longer period.
- e. ethyl cellulose + 5% Mg(OH)2 as interior coating of cans
slow leaching
Mg(OH)2 medium, ~pH 5.0
Chlorophyllase
Recall: chlorophyll chlorophyllide
opt. temp 60-82.2C (more stable than chlorophyll)
Blanching inactivates enzymes if high temperature is used (one of the purposes of blanching)
Optimum temperature for chlorophyllase activity
10
Commercial forms of copper metallo complexes
Copper chlorophyll = copper + pheophytin
Copper chlorophyllin = copper + pheophorbide
FAO of UN certified the use of copper metallic complexes as safe in foods provided no more than 200
ppm (mg/kg) of free ionizable copper present
Veri-green refers to blanching vegetables in water with Zn or Cu salts to raise tissue concentration
of metal to 100-200 ppm
Direct adding of Zn/Cu ions in canning brine had no significant effect on chlorophyll
- best process to retain green color in vegetables
- blanch in the presence of Zn ions
- increase membrane permeability by heating tissues to 60C before blanching
- provide the right pH, i.e., favors metallo complexes
use anions to alter surface change of issue
- recall effect of surface active detergents
FEB 09
FLAVONOIDS
- subgroup under phenolic compounds
- widely distributed in plants
- associated with the yellow color in some plants; also responsible for the whiteness in some plants; also
impart the following colors: blue, purple, magenta, red, orange, due to anthocyanins
- carbon skeleton: basic C6C3C6 structure
- color depends on the substituents on rings A & B
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1. Remove the OH at (1): flavone
2. Replace OH at (1) with Zn ring: isoflavone
3. Replace the O at (2) with a H: anthocyanin
4. Replace the OH at (3) with glucose;
Remove OH at (4) ;
Remove OH at (1): glucoside
(glycoside if exact sugar is not specified)
ANTHOCYANIN
- most prevalent flavonoid
- Greek words: anthos flower; kyanos blue
- Impart a wide range of colors in plants: blue, purp[le, magenta, red, orange
Most notable investigators (Nobel prizes in Chemistry) in part of work in plant pigments
1. Robert Robinson (1886-1975)
2. Richard Willstatter (1872- 1942)
There are 250 anthocyanins in plants, content vary from about 20mg/100g to 600mg/100g fresh weight
Q. Which is responsible for the color in fruits, flowers, leaves (or any plant part)?
A. Distinctive color in the plant part: often due to a combination or a system of pigments*
*usually 4-6 pigments, one may predominate
Examples:
1. Simple System
blackberries contain primarily cyanidin-3-glucoside
2. Complex System
blueberries contain 15 pigments
R1, R3 H, OH or OCH3
R2 OH
R4 glycosyl
R5 H or glycosyl
ANTHOCYANINS IN PLANTS
- exist as glycosides of polyhdroxy and/or polymethoxy derivatives of the flavylium salts
- differ in the R groups:
*no. of hydroxyl or methoxy groups
*types, no. and site of attachment of sugars to the molecule
*types and no. of aliphatic or aromatic acids attached to the sugars (some contain organic acids &
metals Al, Fe, Mg)
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HYDROLYSIS OF ANTHOCYANINS
hydrolysis
anthocyanin anthocyanidin + sugar
SUGARS:
1. glucose
2. galactose
3. arabinose
4. xylose
5. rhamnose
Anthocyanidin
Top to bottom: increasing redness; increasing no. of OCH3 (methoxy group) *see column 2 & 3
Left to right: increasing blueness; increasing no of OH (hydroxyl group) *see row 1
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FEB 13
Explain observation: Bathochromic changes
Deepening of hue is due to the bathochromic change (i.e., longer wavelength) light absorption band in the
visible spectrum shifts from violet through red to blue
AUXOCHROME
- (auxanein) to increase and (chroma) colour
- is a group of atoms attached to a chromophore which modifies the ability of that chromophore to
absorb light
BATHOCHROMIC CHANGE
*e- donating; *has bathochromic effect
In anthocyanidins:
R groups: hydroxyl, OH and methoxy, OCH3
Compare bathochromic effect of OH and OCH3
OCH3 has greater e- donating capacity than OH -> cause greater bathochromic effect
HYPSOCHROMIC CHANGE opposite change
PROPERTIES OF ANTHOCYANINS
Solubility water soluble
Note: anthocyanidin less water soluble than anthocyanins
Chemical properties readily undergo changes with pH changes
- relatively unstable, degraded during extraction, processing, storage
STABILITY OF ANTHOCYANINS
Recall: structure and substituents (subgroups) on the aglycone (anthocyanidin)
Monoglucoside vs Diglucoside
Examples:
Cyanidin-3-rutinoside 16
TYPE OF SUGAR
Anthocyanin containing galactose shown to be more stable than anthocyanin containing arabinose in
stored cranberry (Starr and Francis, 1968)
Note: Substituents (1-3 [OH, OCH3, sugar]) do not react but influence marked effect on stability.
B. TEMPERATURE
- rate of degradation is influenced by pH, O2 and structural conformation
- structural features which increase pH stability, also increase thermal stability
C. OXYGEN
- anthocyanins are unsaturated, readily undergo oxidation
- manifestations: browning of some fruits or its products
*Aw of dried fruits/vegetables, if there is minimal degradation of anthocyanins during drying, such
will be preserved, hence color will be maintained
Prevention of Oxidation:
- exclusion or removal of oxygen during drying: vacuum drying, freeze drying
*Processing:
1. proper exhausting before sealing of canned/bottled products
2. processing under nitrogen atmosphere or under vacuum
3. packaging in nitrogen atmosphere (e.g. powdered grape juice)
4. vacuum packaging
D. LIGHT
- accelerates anthocyanin degradation
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Comparison of anthocyanin stability in the presence of light
E. CONCENTRATION
FEB 27
2. MINOR FACTORS
A. DEGRADATIVE ENZYMES
Two groups implicated
1. Glycosidases generally referred to as anthocyanases however substrates acted are not
2. Polyphenol oxidases limited anthocyanins hence use of term is not encouraged
glycosidase
anthocyanins sugar + anthocyaninidin loss of color intensity*
*results from:
1. Formation of colorless products
2. Loss of solubility of anthocyanidin
-> polyphenol oxidase (PPO) oxidize/degrades anthocyanins in the presence of o-diphenol and
oxygen
-> not directly act/oxidize anthocyanins; oxidize o-diphenol and product formed reacts with
anthocyanins
Steps:
PPO
1. o-diphenol + O2 o-benzoquinone
2. o-benzoquinone + anthocyanin oxidized anthocyanin + degradation products
brown products
1 enzymatic 2 chemical
B. ASCORBIC ACID
- degradative motion on anthocyanins is indirect; it undergoes oxidation and products degrade
anthocyanins
Cu++
ascorbic acid ------- H2O2
cleaves pyryllium ring by a nucleophilic attack at C2
anthocyanin + H2O2 ---------> colorless esters + coumarin derivatives ---> brown precipitate*
*occurs in some juices
C. SULFUR DIOXIDE
- used in food processing*
*as preservative: 500 ppm to 2000 ppm
*as bleaching agent: higher concentration; 0.8-15%
Ex. production of maraschino or candied & glace cherries
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Effect of SO2 loss of color
Reversible or irreversible?
Reversible: color can be restored through desulfuring , i.e., wash off SO2 before further processing
Reaction:
anthocyanin + SO2 ------> complex formation (colorless)
Suggested reaction: SO2 attacks C4
Note:
1. Some anthocyanins are resistant to bleaching; C4 is blocked or exists as dimmers linked
through C4
2. Irreversible in maraschino or candied cherries
D. METAL IONS
Anthocyanin + metal complex
In food processing, e.g., canning, metal anthocyanin complex formation may occur*
*desirable or undesirable
Note:
Not all anthocyanins have vicinal phenolic hydroxyl groups, hence metal complexation can be
used to differentiate groups of anthocyanins
Mechanism in pinking:
heat; acidic conditions metal
Proanthocyanidin anthocyanins metal-anthocyanin complex
(colorless) (pink)
E. SUGARS
Effect on anthocyanins depends on sugar concentration; beneficial or not
Low sugar concentrations, i.e., at concentration with little or negligible effect on Aw -> accelerate
anthocyanin degradation
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Types of sugar -> varying effect
Fructose
Arabinose FALSor greater degradation
Lactose
Sorbose
Glucose
Sucrose MGSuc (or MSG) less degradation
Maltose
EFFECT OF COPIGMENTATION
- either accelerate or retard depending on the situation
- the negatively charged sulfonates and the positively charged flavylium cations form intermolecular ring
interactions
PREVENTION OF PHOTODEGRADATION:
*Proper packaging, e.g. dark colored bottles or plastic films
Ionizing radiation degrades anthocyanins
OTHER FLAVONOIDS
- non-anthocyanin type flavonoids
- impart a range of color to plants and food
yellow: yellow flavonoids
xanthos yellow
- whiteness of some plant materials
- brown or black due to the oxidation products of phenolic groups (occur in nature)
>>classes of non-anthocyanin type flavonoids (differences is based on the state of oxidation of the 3-
carbon link)
PROPERTIES
- with light absorption characteristics
- differ due to differences in degree of unsaturation
- also influenced by the acylation and/or glycosylation
- involved in copigmentation
- metal chelators
chelation or reaction with metal; influence color formation
Ex. Luteolin + Al -------> yellow complex
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IMPORTANCE IN FOODS:
1. Color, particularly in copigmentation
Ex.
>whiteness: in onions, cauliflower, potato
2. Antioxidant properties
- ability to sequester metal
MAR 02
4. Potential sweetener
>citrus, has naringen* bitter
*a flavanone potential sweetener
5. Deodorizer
>tannins and flavonoids from chestnut inner shell, shown to have antioxidant and deodorizing
activities
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