BIOCHEMISTRY molecular and structural formulas but differ in the
orientation of atoms in space).
Biochemistry is the study of the chemical substances
found in living organisms and the chemical interactions
of these substances with each other.
Bioorganic substances (contains carbon) include
carbohydrates, lipids, proteins and nucleic substances.
CARBOHYDRATES
 From hydrate of carbon Cn(H2O)n which is now
known to be incorrect
 Most abundant class of bioorganic molecules in
planet Earth although their abundance in the body
is relatively low (2%)
 In plants, carbohydrates are produced as cellulose
(structural elements) or starch (energy reserves)
 Carbohydrate is a polyhydroxyaldehyde (R-CHO),
a polyhydroxyketone (R-CO-R) or a compound that
yields polyhydroxyaldehydes or
polyhydroxyketones upon hydrolysis.
FUNCTIONS IN HUMANS
1. Oxidation provides energy
2. Glycogen provides short-term energy reserve
3. Supply carbon atoms for the synthesis of other
biochemical substances
4. Form part of structural framework of DNA and
RNA molecules
5. Component of cell membrane (w/ lipids)
6. Functions in a variety of cell-cell and cell-
molecule recognition processes (with proteins)
CLASSIFICATIONS: monosaccharide, disaccharide,
oligosaccharide (3-10), and polysaccharide
CHIRALITY: Handedness in Molecules
 Nonsuperimposable mirror images exist in “left-
handed” and “right-handed” forms.
 Chiral center* is an atom in a molecule that has 4
different groups bonded to it in a tetrahedral
orientation (requirement for handedness)
 In human-body chemistry, it is found that right-
handed and left-handed forms of a molecule
usually elicit different response and that our bodies
can normally use only one of the two forms of a
chiral compound. (Studies show that the body’s
response to the right-handed form of the hormone
epinephrine is 20 times greater than its response
to the left-handed form).
STEREOISOMERISM: Enantiomers and
Diastereomers
 Constitutional isomers are compounds that have
the same molecular formula and different
connectivity.
 Left- and right-handed forms of a chiral molecule
are stereoisomers (isomers that have the same
 Enantiomers are stereoisomers whose molecules
are nonsuperimposable mirror images of each
other (e.g. left- and right-handed forms)
 Diastereomers are stereoisomers whose
molecules are not mirror images of each other (e.g.
cis-trans isomers)
 Cis–trans isomerism, also known as geometric
isomerism or configurational isomerism are
diastereomers that results from restricted rotation
about chemical bonds
FISCHER PROJECTION FORMULA
 Handedness is specified using D and L
designations from Latin dextro, which means “right”
and levo, which means “left”.
 The D,L nomenclature gives the configuration
(handedness) only at the highest numbered chiral
center (see where –OH is attached).
 Epimers are diastereomers whose molecules
differ only in the configuration at one chiral center.
 The formula 2n gives the maximum possible
number of stereoisomers for a molecule with n
chiral atoms. In a few cases, the actual number of
stereoisomers is less than the maximum because
of symmetry considerations that make some mirror
images superimposable.
 An enantiomer that rotates plane-polarized light in
a clockwise direction is said to be dextrorotatory.
A levorotatory compound is a chiral compound
that rotates the plane of polarized light in a counter
clockwise direction.
CLASSIFIATION OF MONOSACCHARIDES
Monosaccharides and disaccharides are often called
sugars.
Based on carbonyl group present:
1. Aldose
-contains an aldehyde functional group
(polyhydroxyaldehyde)
2. Ketose
- contains an ketone functional group
(polyhydroxyketone)
 Based on number of carbon atoms: -synthesized from glucose in the mammary glands for
use in lactose (glucose + galactose)
-called brain sugar because it is a component of
glycoproteins found in brain and nerve tissue
-also present in the chemical markers that distinguish
various blood types
4. D-Fructose (LRR)
-biochemically most important ketohexose
-also called levulose (aqueous solutions of naturally
occurring D-fructose rotate plane-polarized light to the
left) and fruit sugar (sweetest tasting of all sugars,
present in many fruits and honey)
-sometimes used as a dietary sugar because less is
needed for the same amount of sweetness
5. D-Ribose (RRR)
-component of complex molecules including ribonucleic
acids (RNAs) and energy-rich compounds such as
adenosine triphosphate (ATP)
-compound 2-dioxy-D-ribose is a component of DNA
molecules
CYCLIC FORMS
 The cyclic forms of monosaccharides result from the
ability of their carbonyl group to react intramolecularly
with a hydroxyl group. Structurally, the resulting cyclic
compounds are cyclic hemiacetals (having both –OH
and –OR group attached to the same carbon atom).

Cyclic Forms of D-Glucose

1. All hydroxyl groups drawn to the right in the Fischer
projection formula appear below the ring. Those to the left
above the ring.
2. Counter clockwise rotation of the groups attached to
C5. –OH group on C5 adds to C1.
3. Two possible stereoisomers depending on how ring
closure occurs.

Biochemically Important Monosaccharides

1. D-Glyceraldehyde and Dihydroxyacetone
-important intermediates in the process of glycolysis
2. D-Glucose (RLRR)
-most abundant in nature
-referred to as grape sugar because it is abundant in ripe
fruits particularly ripe grapes (20%-30% glucose by
mass)
-also known as dextrose (optically active D-glucose, in
aqueous solution, rotates plane-polarized light to the
right) and blood sugar (blood contains dissolved
glucose with normal conc of 70-100 mg/dL, 130 mg/dL
on the first hour after eating) *1 dL= 100 mL
-5% (m/v) glucose solution is often used in hospitals as
an intravenous source of nourishment for patients who
canot take food by mouth
-cells use glucose as a primary source of energy
-insulin and glucagon keep blood glucose concentration
within normal range (otherwise diabetes) α-D-Glucose if –OH attached to C1 is on the opposite side
3. D-Galactose (RLLR) of the ring as –CH2OH attached to C5, but if on the same
-epimer of D-glucose differing only in the configuration of side, β-D-Glucose.
the –OH and –H group on carbon 4
 Anomers are cyclic monosaccharides that differ only
in the positions of the substituents on the anomeric
carbon atom.
Cyclic Forms of D-Ribose and D-Fructose

 Aldoses are called reducing sugars because they

act as reducing agents in reactions with Tollen’s
solution, glucose reduces Ag+ ion to Ag, and with
 A cyclic monosaccharide containing a six-atom ring
Benedict’s solution, glucose reduces Cu2+ to Cu+
is called pyranose, and one containing five-atom
ion.
ring is called furanose because their ring
 Under basic conditions, ketoses are also reducing
structures resemble the ring structures in the cyclic
sugars. Ketose undergoes structural
ethers pyran and furan respectively.
rearrangement that produces an aldose, and the
HAWORTH PROJECTION aldose then reacts. Thus all monosaccharides are
 A Haworth Projection formula is a two-dimensional reducing sugars.
structural notation that specifies three-dimensional  In biochemical systems, enzymes can oxidize the
structures of a cyclic form of a monosaccharide. primary alcohol end of an aldose w/o oxidation of
 The D or L form of a monosaccharide is determined the aldehyde group, to produce an alduronic acid.
by the position of the terminal -CH2OH group on the
highest numbered ring carbon atom: in D form the
group is positioned above the ring while in L form,
the group is positioned below the ring.
 α or β configuration is determined by the position
of the –OH group on C1 relative to the -CH2OH
group that determines D or L series. In β
configuration, both groups point to the same
 Strong oxidizing agents can oxidize both ends of a
direction while in α configuration, the two groups
monosaccharide at the same time to produce a
point in the opposite direction.
polyhydroxydicarboxylic acids known as aldaric
acid.

 In situations where α or β configuration does not

matter, the —OH group on carbon 1 is placed in a
horizontal position, and a wavy line is used as the
bond that connects it to the ring.
2. Reduction to Produce Sugar Alcohols
 The carbonyl group present in monosaccharide
can be reduced to a hydroxyl group using hydrogen
 Lastly, add the –OH groups of the remaining as the reducing agent. The product of the reduction
carbon atoms. The –OH group is drawn down if it’s is the corresponding polyhydroxyalcohols called as
to the right of the Fischer projection formula while sugar alcohols or alditols.
if it’s drawn to the left, it is drawn up.
REACTIONS OF MONOSACCHARIDES

1. Oxidation to produce acidic sugars 3. Glycoside Formation

 Weak oxidizing agents, such as Tollen’s and  The cyclic forms of monosaccharides are
Benedict’s solutions, oxidize the aldehyde end of hemiacetals and they react with alcohols to form
monosaccharide to produce aldonic acid. acetals. A glycoside is an acetal formed from a
 cyclic monosaccharide by replacement of the
hemicatal carbon –OH group with an –OR group.
4. Phosphate Ester Formation
 The hydroxyl groups of a monosaccharide can
react with inorganic oxyacids to form inorganic
esters.
5. Amino Sugar Formation
 Formed if one of the hydroxyl groups of a
monosaccharide is replaced with an amino group.
 The N-acetyl derivatives of D-Glucosamine and D-
Galactosamine are present in the biochemical
markers on red blood cells, which distinguish the
various blood types.
DISACCHARIDES
1. Maltose (Malt Sugar)
 Produced whenever the polysaccharide starch
breaks down, as happens in plants when seeds
germinated and in human beings during starch
digestion
 Common ingredient in baby food and malted milk
 Malt (germinated barley that has been baked and
ground) contains maltose
 Made up of 2 D-Glucose units, one of which must
be α-D-Glucose
 Maltose is a reducing sugar because the glucose
unit on the right has a hemiacetal carbon atom
(C1). Thus this glucose can open and close.
 The most important chemical reaction of maltose
is that of hydrolysis which produces two molecules
of D-Glucose. Anacidic environment or the
enzyme maltase is needed for hydrolysis to occur.
2. Cellobiose
 Produced as an intermediate in the hydrolysis of
the polysaccharide cellulose
 Contains 2 D-Glucose monosaccharide units, but
the D-Glucose functioning as a hemiacetal must
have β configuration.
 Thus, the result is a β (1,4) glycosidic linkge
 It is also a reducing sugar
 Both the human body and yeast lack the enzyme
cellobiase needed to break the glycosidic bond of
cellobiose. Thus, it can not be digested by humans
or fermented by yeast.
3. Lactose (milk sugar)
 Made up of β-D-Galactose unit and a D-Glucose
unit joined by a β (1,4) glycosidic linkage
 The glucose hemiacetal center is unaffected when
galactose bonds to glucose in the formation of
lactose, so lactose is a reducing sugar (the glucose
ring can open to give an aldehyde)
 Souring of milk is cause by the conversion of
lactose to lactic acid by bacteria in the milk
 Pasteurization of milk is a quick heating process
that kills most bacteria and retards souring process
 Can be hydrolysed by acid or by enzyme lactase
4. Sucrose (Table Sugar)
 Most abundant of all disaccharides
 α-D-Glucose + β-D-Glucose
 α, β (1,2) glycosidic linkage (head-to-head) unlike
the head-to-tail linkages of the other
disaccharides
 Sucrose is a non-reducing sugar because the
hemiactal center (anomeric carbon atom) of each
monosaccharide is involved in the glycosidic
linkage
 Sucrase, the enzyme needed to break the α, β
(1,2) linkage in sucrose is present in the human
body
 Sucose hydrolysis produces an equimolecular
mixture of glucose and fructose called invert
sugar (sweeter than sucrose)
 Honeybees and other insects possess an enzyme
called invertase that hydrolyzes sucrose to invert
sugar
OLIGOSACCHARIDES
 Three to ten monosaccharide units
 Naturally occurring oligosaccharides found in
vegetables (onions, cabbage, broccoli, brussel
sprouts, whole wheat, beans) are raffinose (α-D-
Galactose, α-D-Glucose, β-D-Fructose) and
stachyose (α-D-Galactose, α-D-Galactose, α-D-
Glucose, β-D-Fructose). Humans lack the digestive
enzymes to metabolize either. So both pass
undigested into the large intestines where bacteria
act upon them. The bacterial action produces
discomfort and flatulence
 In biochemical systems, it is more common to
encounter oligosaccharides as components of
more complex molecules; the type of blood a
person has is determined by the type of
oligosaccharide that is attached to a person’s RBC
(biochemical markers).
 Solanine, a compound found in potato plant, is a
plant toxin against insects and predators. The small
amount of solanine in properly stored potatoes is
not dangerous and actually contributes to its
flavour (excessive amounts of solanine makes
potatoes taste bitter). In improperly stored
potatoes, green color develops in their skin and the
flesh just under the skin which indicates high levels
of solanine. The color comes from chlorophyll
which sunlight exposure also stimulates. Peeling
potatoes deeply to remove the green color also
removes excess solanine. Since solanine
production also increases when potatoes sprout,
removing the sprout and potato “eyes” also
removes excess solanine. Deep frying and
microwaving are also effective in diminishing these
levels but boiling it is not. *Solanine trisaccharide’s
structure involves D-Glucose, D-Galactose, L-
Rhamnose
 Artificial Sweeteners: Saccharin, Aspartame,
Sucralose, Neotame
POLYSACCHARIDES (Glycans)
 A homopolysaccharide is a polysaccharide in
which only one type of monosaccharide monomer
is present. A heteropolysaccharide whose
structures contain two or more types of
monosaccharide monomers include hyaluronic
acid and heparin.
 The ability to form branched-chain structures
distinguishes polysaccharides from the other two
types of biochemical polymers: proteins and
nucleic acid which occur only as linear polymers.
 In nutrition discussions, monosaccharides and
disaccharides are called simple carbohydrates
while polysaccharides are called complex
carbohydrates.
 Unlike monosaccharides, and most disaccharides,
polysaccharides are not sweet and do not test
positive in Tollens and Benedict’s solutions. They
have limited water solubility because of their size.
However, the –OH groups present can individually
become hydrated by water molecule. The result is
usually a thick colloidal suspension of the
polysaccharide in water. Polysaccharides, such as
 flour and cornstarch, are often used as thickening
agents in sauces, desserts, and gravy
STORAGE POLYSACCHARIDES
Polysaccharide that is a storage form for
monosaccharide and is used as an energy source
in cells
1. Starch
 Homopolysaccharide containing only glucose
monosaccharide units. It is the energy storage in
plants.
 If excess glucose enters a plant cell, it is converted
to starch and stored for later use. When the cell
cannot get enough glucose from outside the cell, it
hydrolyzes starch to release glucose.
 Most starch consist of polyglucose
polysaccharides: amylose (straight-chain glucose
polymer) and amylopectin (glucose polymer with
branch occurring once every 25-30 glucose units)
 Iodine is often used to test for the presence of
starch in solution. Starch-containing solutions turn
blue-black when iodine is added because the
helical amylose forms a charge-transfer complex
with polyiodide that absorbs light of a different
wavelength and the complimentary color is
observed by the human eye.
2. Glycogen
 Polysaccharide containing only glucose units. It is
the glucose storage polysaccharide in humans and
animals. Referred to sometimes as animal starch.
 Glycogen has a structure similar to that of
amylopectin; all glycosidic linkages are α (1,4) and
α (1,6), but glycogen is about three times more
highly branched than amylopectin, and it is much
larger, with up to 1,000,000 glucose units present
 When excess glucose is present in the blood
(usually from eating too much starch), the liver and
muscle tissue convert the excess glucose to
glycogen, which is then stored in these tissues.
Whenever the glucose level drops (from exercise,
fasting, or normal activities), some stored glycogen
is hydrolysed back to glucose.
 Glycogen is an ideal form of glucose. The large
size prevents them from diffusing out of the cell.
Also, conversion of glucose to glycogen reduces
osmotic pressure preventing cells from bursting.
High concentrations of glycogen in a cell
sometimes precipitate or crystallize into glycogen
granules.
STRUCTURAL POLYSACCHARIDES
Polysaccharide that serves as a structural element in
plant cell walls and animal exoskeletons
1. Cellulose
 Structural component of plant cell walls, most
abundant naturally occurring polysaccharides
 High concentrations in “woody” portions of plants
 Unbranched glucose polymer with β (1,4) linkages
 Linear structure of cellulose molecules, when
aligned side by side, becomes water-insoluble
fibers because of interchain hydrogen bonding
involving numerous hydroxyl groups present
 The intestinal tracts of grazing animals and
termites contain bacteria that produce cellulase,
an enzyme that can hydrolyze cellulose β (1,4)
linkages and produce free glucose for their
nutrition.
 Despite its nondigestibility, cellulose is still an
important component of a balanced diet serving as
dietary fiber. Dietary fiber provides the digestive
tract with “bulk” that helps the food move through
the intestinal tract and facilitates the excretion of
solid wastes. Cellulose readily absorbs water,
leading to softer stools and frequent bowel action.
 High-fiber food may also play a role in weight
control. Some dietary fibers bind lipids such as
cholesterol and carry them out of the body with
feces. This lowers blood lipid concentrations and,
possibly, the risk of heart and artery disease.
2. Chitin
 Give rigidity to the exoskeletons of crustaceans
and other arthropods. It also occurs in the cell walls
of fungi
 Structurally, it is similar to cellulose but the
monosaccharide present in chitin is an N-acetyl
 amino derivative of D-glucose (N-acetyl-β-D-
glucosamine).
ACIDIC POLYSACCHARIDES
 Polysaccharide with a disaccharide repeating unit
in which one of the disaccharide components is an
amino sugar and one or both disaccharide
components has a negative charge due to a
sulphate group or a carboxyl group.
1. Hyaluronic Acid
 The structure of hyaluronic acid contains
alternating residues of N-acetyl-β-D-glucosamine
(NAG) and D-glucuronate (carboxylate ion formed
when D-glucuronic acid loses its acidic hydrogen
atom).
 Alternating patterns of β(1,3) and β(1,4) linkages
 Highly viscous hyaluronic acid solutions serve as
lubricants in the fluid of joints and they are also
associated with the jelly-like consistency of the
vitreous humor of the eye. (from Greek hyalos
glass because of its glass-like appearance)
2. Heparin
 The monosaccharides present in the disaccharide
repeating unit are D-glucuronate-2-sulfate and N-
sulfo-D-glucosamine-6-sulfate, both of which
contain two negatively charged acidic groups.
 Heparin is a blood anticoagulant. It is naturally
present in mast cells and is released at the site of
tissue injury. It prevents formation of clots in blood
and retards the growth of existing clots but does not
break down existing clots.
 Pharmaceutical-grade heparin is applied as an
anticoagulant to the interior/exterior of external
objects that come in contact with blood (test tubes,
prosthetic implant, dialysis machine surface). The
source for pharmaceutical heparin is intestinal or
lung tissue of pigs and cows.
 Heparin is a small polysaccharide with only 15-90
disaccharide residues per chain.
DIETARY CONSIDERATIONS AND
CARBOHYDRATES
 A balanced diet should ideally be 60%
carbohydrate.
 Energy content from simple carbohydrate can
come from natural sugars and refined sugars
added to food. A natural sugar is a sugar naturally
present in whole foods (e.g. milk, fruits). A refined
sugar is a sugar that has been separated from its
plant source (pure form).
 Refined sugars are often said to provide empty
calories because they provide energy but few other
nutrients. A tablespoon of sucrose provides 50
calories of energy just as a small orange does but
latter also provides Vitamin C, potassium, calcium,
and fiber.
