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BIOCHEMISTRY
BIOCHEMISTRY – is the study of the chemical substances found in living organisms and the
chemical interactions of these substances with each other.
1. Bioinorganic substance – do not contain carbon; Water (70%), inorganic salts (5%)
2. Bioorganic substance – contain carbon; protein (15%), lipids (8%), carbohydrates (2%),
nucleic acid (2%)
CARBOHYDRATE
Carbohydrates – most abundant class of bioorganic molecules; 75% by mass of dry plant
materials
Photosynthesis :
Plants’ 2 main uses for the carbohydrates they produce: cellulose - structural elements; starch-
energy reserves
Function in human:
Classification of carbohydrates:
1. Monosaccharide – contains single polyhydroxy aldehyde or polyhydroxy ketone unit;
cannot be broken into simpler units by hydrolysis reactions. Naturally occurring
monosaccharide have from 3 to 4 carbon atoms; 5 to 6 carbon are common.
Saccharum – Latin word for sugar.
Classification according to the functional group: aldose , ketose
Classification according to the number of carbon: triose, tetrose, pentose, hexose
Structure of Aldoses
Structure of ketoses
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Examples:
In human body chemistry, right-handed and left-handed forms of a molecule often elicit
different responses within the body.
1. Sometimes both forms are biologically active, each form giving different response;
2. sometimes both elicit the same response, but one responses greater than the other;
and
3. sometimes only one of the two forms are biochemically active.
Plants produce only right-handed monosaccharide, building blocks for protein are left-
handed amino acids.
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Assigning of L and D
Examples
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Stereoisomers – isomers that have same molecular and structural formulas but differ in the
orientation of atoms in space.
1.Enantiomers – stereoisomer whose molecules are nonsuperimposable mirror image of
each other. All Left and right handed forms
For molecules to be a mirror image , ALL hydroxyl groups
attached in chiral centers should be in OPPOSITE
orientation for both molecules.
OH in carbon#2: A is on the left; B is on the right
OH in carbon#3: A is on the right; B is on the left
OH in carbon#4: A is on the left; B is on the right
OH in carbon#5: A is on the right; B is on the left
Since, ALL are oriented in OPPOSITE direction
These two structures are enantiomers
2. Diastereomers – stereoisomers whose molecules are not mirror image of each other.
**Epimers – is a type of diastereomers whose molecules differ only in the configuration at
ONE chiral center.
Example:
For molecules to be NOT a mirror image , hydroxyl groups
attached in chiral centers should be arranged in OPPOSITE and
SAME orientation for both molecules.
OH in carbon#2: A and B are same
OH in carbon#3: A is on the right; B is on the left
OH in carbon#4: A is on the left; B is on the right
OH in carbon#5: A and B are same
OH are oriented in OPPOSITE and SAME direction
Examples
Optically active - compound is a compound that rotates the plane of a polarized light.
Achiral molecules are optically inactive and chiral molecules are optically active.
1. Dextrorotatory compounds – a chiral compound that rotates the plane of a polarized
light in a CLOCKWISE direction (+) / Right
2. Levorotatory compounds – a chiral compound that rotates the plane of a polarized light
in a COUNTERCLOCKWISE direction (-) / Left
The handedness of an enantiomer (D and L) and the direction of rotation of a plane-
polarized light by enantiomer [(+) and (-)] are NOT CONNECTED entities. There is no
way of knowing which way an enantiomer will rotate light until it is examined with a
POLARIMETER.
Example: D-(+)-mannose
Example: D-glucose
RULES:
1. All OH, hydroxyl groups in the chiral centers drawn to the RIGHT in the original Fischer
projection formula will appear BELOW the ring in the Haworth projection formula. All
those to the LEFT will appear ABOVE the ring.(OH in highest chiral center will NOT follow
this rule )
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2. Terminal –CH2OH (highest-numbered carbon) group will be ABOVE the ring if the
monosaccharide is a D-form. Terminal –CH2OH group will appear BELOW the ring if L-
form.
3. Rotate groups attached to (second to the last carbon) or (carbon 5) to give an easy
visualization of intramolecular hemiacetal formation. Intramolecular reaction between
hydroxyl (-OH) and carbonyl (C=O).
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Oxygen in hydroxyl (from carbon5) will add across the carbon in the carbonyl group
(C=O) forming a cyclic structure. Carbonyl group’s double bond will be broken into single
bond to meet the four bond requirement. Hydrogen from hydroxyl group (from carbon5)
will add across the oxygen in the carbonyl group (C=O) forming a new hydroxyl
substituent.
ANOMERIC carbon atom – is the hemiacetal carbon atom present in the cyclic
monosaccharide structure. It is bonded to –OH and to –O atom in the heterocyclic ring.
ANOMERS – are cyclic monosaccharides that differ only in the position of the
substituents on the anomeric (hemiacetal) carbon atoms. α (alpha) and β (beta)
ANOMERS.
The D form of a monosaccharide will have two anomers (α and β) after cyclization. The L
form of a monosaccharide will have two anomers (α and β) after cyclization.
3. D-glucose – most abundant in nature; used by the cell as primary source of energy
Other name: ―grape sugar‖- (20%-30% glucose by mass in ripe grapes);
―dextrose‖ - aqueous solution of D-glucose rotates to the right; “blood sugar”,
blood contains dissolved glucose (normal concentration= 70-100mg/dL).
The actual glucose concentration in blood is dependent on the time that has elapsed since
the last meal was eaten. A concentration of about 130 mg/dL occurs in the first hour after
eating, and then the concentration decreases over the next 2-3 hours back to the normal
range. Two hormones, insulin and glucagon have important roles in keeping glucose blood
concentration within normal range, which is required for normal body function. Abnormal
functioning of the hormonal control process for blood glucose levels leads to DIABETES.
REACTION OF MONOSACCHARIDES
1. Oxidation to acidic sugars
a. Use of weak oxidizing agents (Tollens and Benedict solution) to oxidize the
aldehyde end of an ALDOSE to give ALDONIC ACID.
Reducing sugars are carbohydrates that gives positive test with Tollens and Benedict
solutions. All monosaccharide are reducing sugars.
b. Use of strong oxidizing agents to oxidize BOTH ends (the aldehyde end and the
terminal primary alcohol group) of an ALDOSE to give ALDARIC ACID.
c. Use of enzymes to oxidize the terminal primary alcohol end of an ALDOSE to give
ALDURONIC ACID (aldehyde end is unoxidized).
3. Glycoside formation
Glycoside is an acetal formed from a cyclic monosaccharide by replacement of the
hemiacetal carbon’s –OH group with an –OR group. Glycosides can exist in and β forms.
Acetals have two —OR groups attached to the same carbon atom.
SUMMARY
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DISACCHARIDE
When two monosaccharide molecules react to form a glycosidic bond (linkage), a water
molecule is generated in the process through a chemical reaction known as condensation.
Therefore, condensation is a reaction where water is removed and a polymer is formed.
Glycosidic linkage is the bond in a disaccharide resulting from the reaction of the
hemiacetal carbon atom –OH group of one monosaccharide and an –OH group on the other
monosaccharide.
Reaction:
Lactose is the principal carbohydrate in milk. Human mother’s milk obtained by nursing
infants contains 7%-8% lactose, almost double the 4%-5% lactose found in cow’s milk.
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4.Sucrose – common name “table sugar”; contains -D-glucose and β-D-fructose; glycosidic
linkage is ,β (1→2); unlike maltose, cellubiose and lactose, sucrose is nonreducing sugar
and does not have and β isomers because the hemiacetal center/ anomeric carbon atoms
are involve in the glycosidic linkage ; invert sugar are equimolar mixture of glucose and
fructose and the product of sugar hydrolysis during digestion and cooking; sucrase is the
enzyme needed for sucrose hydrolysis.
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Because of the high caloric value of sucrose, it is often difficult to satisfy a demanding ―sweet
tooth‖ without adding pounds to the body frame. As a solution to ―sucrose problem‖, sugar
substitutes are now used since they provide virtually no calories. Three sugar substitutes
which have been widely used are saccharin, sodium cyclamate and aspartame. However,
these SUGAR SUBSTITUTES have received much publicity because of their safety.
SUGAR SUBSTITUTES
1. Saccharin – oldest artificial sweeteners; study suggested that large dose of saccharin
caused bladder tumors in rats; It is 300 times sweeter than sucrose but has a bitter
aftertaste.
2. Sodium cyclamate - study suggested that it can cause cancer among laboratory
animals; Canada has approved the use of sodium cyclamate but banned saccharin. It is
30 times sweeter than sugar.
3. Aspartame – Nutra-Sweet; 150 times sweeter than sucrose; aspartame and saccharin
are NOT heat-stable therefore must not be used in products that require cooking; it
contains phenylalanine, an amino acid that cause mental retardation among children
suffering from PKU (phenylketonuria)
4. Sucralose – 600 times sweeter than sucrose; heat-stable, does not lose its sweetness
when heated; it is calorie-free, cannot be hydrolyzed in digestive tract;
5. Neotame – 7000 times sweeter than sucrose; general-purpose sweetener; heat-stable;
an aspartame derivate but is safe for PKU
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OLIGOSACCHARIDE
( )
found in onion, cabbage, broccoli, whole wheat, bean
( )}
Human lacks the digestive enzymes necessary to metabolize raffinose and stachyose, hence
when ingested, they pass undigested into large intestine, where bacteria act upon them
usually produces discomfort and flatulence (gas).
SOLANINE – compound contains oligosaccharide, found in potato and act as plant’s toxin to
defense against insects and predators. Small amount of solanine present in properly
stored potatoes is not dangerous and actually contributes to the flavor. When excessive
solanine is present, potatoes taste bitter. Improperly stored potatoes (exposed to sunlight),
solanine and chlorophyll increases. Deep-frying reduces solanine levels but not in boiling.
A √ X √ x x is incompatible
B X √ √ x
AB X X √ x
TYPE
O √ √ √ √
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The biochemical basis for the various types of blood involves OLIGOSACCHARIDE
molecules (biochemical markers) that are attached to the plasma membrane of the red
blood cells.
POLYSACCHARIDE
POLYSACCHARIDE- Also called glycans; contains monosaccharide units in a polymer chain
Properties:
1. Not sweet
2. Negative in Tollens and Benedict’s solution
3. Has limited solubility in water; thick colloidal suspension in water
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Amylopectin
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Monomer of Heparin