BIOCHEMISTRY

Study of the chemical substances found in living

organisms and the chemical interactions of these
substances with each other.
o How cells are manufactured
o How chemical reactions maintain life
BIOCHEMICAL SUBSTANCE
A chemical substances found within a living
organism.
Divided into two groups:
o Bioinorganic substances substances that
do not contain any carbon
Water (~70%), Inorganic salts (~5%)
o Bioorganic substances substances that
contain carbon
Proteins
(~15%),
Lipids
(~8%),
Carbohydrates (~2%), Nucleic Acids
(~2%)
OCCURRENCE
AND
FUNCTION
OF
CARBOHYDRATES
Carbohydrates Most abundant class of
bioorganic molecules on planet Earth; constitute
about 75% by mass of dry plant materials

Green plants (which contain chlorophyll), produce

carbohydrates via photosynthesis.
CO2 + H2O + solar energy Carbohydrates + O2
o In it arrow, chlorophyll and plant enzymes
Two main uses of carbohydrates for plants
o As a cellulose, it serves as a structural
element
o As a starch, it provides energy reserves for
the plants

Dietary intake of plant materials is the major

carbohydrate source for humans and animals.
Functions of carbohydrates for humans:
o Carbohydrate oxidation provides energy.
o Carbohydrate storage, in the form of
glycogen, provides a short-term energy
reserve.
o Carbohydrates supply carbon atoms for the
synthesis of other biochemical substances
o Carbohydrates form part of the structural
framework of DNA and RNA molecules.
o Carbohydrates linked to lipids are structural
components of cell membranes.
o Carbohydrates linked to proteins function in
a variety of cell-cell and cell-molecule
recognition process.

CLASSIFICATION OF CARBOHYDRATES
General Formula: CnH2nOn or Cn(H2O)n
Hydrate of carbon
Definition: A polyhydroxy aldehyde, a polyhydroxy
ketone, or a compound that yields polyhydroxy
aldehydes
or
polyhydroxy
ketones
upon
hydrolysis.
o Glucose - polyhydroxy aldehyde
o Fructose - polyhydroxy ketone
The two examples structures are representative of
all simple carbohydrates.
o Notable feature: There is a presence of a
functional group on each carbon atom
present.
Monosaccharides
A carbohydrate that contains a single polyhydroxy
aldehyde or polyhydroxy ketone unit

Stoker, H.S. (2016). General, Organic, and Biological Chemistry: Seventh Edition. Cengage:USA.

o Cannot be broken down into simpler units by

hydrolysis
o Examples: Glucose and Fructose
Usually have three to seven carbon atoms
o Five and six-carbon species are common
In PURE form, they are water-soluble, white,
crystalline solids.

Disaccharide
A carbohydrate that contains two monosaccharide
units covalently bonded to each other
They are also crystalline, water-soluble.
o Examples: Sucrose (table sugar) and
Lactose (milk sugar)
Hydrolysis of a disaccharide produces two
monosaccharide units.
Oligosaccharide
A carbohydrate that contains three to ten
monosaccharide units covalently bonded to each
other
o Free
oligosaccharides
are
seldom
encountered in biochemical systems.
Found associated with proteins and lipids
Complete hydrolysis: Several monosaccharide
units

CHIRALITY: HANDEDNESS IN MOLECULES

Handedness in form of isomerism
Not just restricted to carbohydrates. This is a
general phenomenon in all classes of organic
compounds.
Exist in two forms:
o Left-handed and Right-handed
o Its relationship is a mirror image.
Mirror Images
Is the reflection of an object in a mirror
Can be divided into two classes:
o Superimposable mirror images images
that coincide at all points when the images
are laid upon each other
o Nonsuperimposable mirror images images
where not all points coincide when the
images are laid upon each other.
Chirality
Requirements: Carbon atom should have four
different groups boned to it in a tetrahedral
orientation, and should have single bonds only.
o This possesses handedness.
o The carbon atom with the right chirality
requirement is called a chiral center.
Chiral center an atom in a molecule
that ahs four different groups boned to
it in a tetrahedral orientation.
A molecule that contains a chiral center is said to
be chiral.
o Chiral molecule a molecule whose mirror
images are not superimposable; have
handedness

Polysaccharide
A polymeric carbohydrate that contains many
monosaccharide units covalently bonded to each
other.
o Number varies from a few hundred to over
50,000 units.
Undergoes
hydrolysis
under
appropriate
conditions to produce monosaccharide.
o Examples: Cellulose and Starch
Stoker, H.S. (2016). General, Organic, and Biological Chemistry: Seventh Edition. Cengage:USA.

o Achiral molecule a molecule whose mirror

images are superimposable; do not possess
handedness
Simplest chiral organic molecule: trisubstituted
methane
molecule
(e.g.:
Bromochloroiodomethane)

Guidelines for Identifying Chiral Centers

Carbon atom must have four different groups
attached.
A carbon atom involving multiple bonded cannot
be a chiral center. It should be all single bonds.
The commonly encountered entities such as CH 3
and
CH2 in a structural formula never involve a chiral
center because of multiple hydrogen atoms.
For those in a ring system, as long as it does not
have any multiple bonding, it can have a chiral
center. Divided the ring into two:
o It will be a chiral center when both the two
substituents are different
o The two halves of the ring should be
different.

o Six-carbon monosaccharide with aldehyde

Aldohexose

Often called sugars associated with the term

sweetness
o But not all have a sweet taste.
o Sugar a general designation for either a
monosaccharide or a disaccharide
Review differences of monosaccharides Figure 1814 and Figure 18-15.

BIOCHEMICALLY IMPORTANT MONOSACCHARIDES

D-Glyceraldehyde and Dihydroxyacetone
o Important intermediates in the process of
glycolysis, a conversion of glucose into two
molecules of pyruvate.
D-Glucose
o Most abundant in nature
o Found in ripe fruits. (e.g.: Grapes, grape
sugar)
o Also called dextrose and blood sugar
o Two hormones, insulin and glucagon, have
important roles in keeping glucose blood
concentration within normal range.
Read about next topics in book. Skipping to
D-Galactose
Monosaccharides
o Synthesized from glucose in the mammary
CLASSIFICATION OF MONOSACCHARIDES
glands for use in lactose.
Classified as aldoses or ketoses
o Also called as brain sugar, because it is a
o Aldose monosaccharide that contains an
component of the glycoprotein found in
aldehyde functional group; polyhydroxy
brain and nerve tissue
aldehydes
o Also present in blood as a chemical marker
o Ketose monosaccharide that contains a
for A, B, AB and O.
ketone
functional
group;
polyhydroxy
D-Fructose
ketones
o Most important ketohexose
Classified by both their number of carbon atoms
o Also called levulose and fruit sugar.
and their functional group
o Used as a dietary sugar.
Stoker, H.S. (2016). General, Organic, and Biological Chemistry: Seventh Edition. Cengage:USA.
3

D-Ribose
o Component of a variety of complex
molecules
Two of which are the RNA and the ATP

CYCLIC FORMS OF MONOSACCHARIDES

Result from the ability of their carbonyl group to
react intramolecularly with a hydroxyl group. The
resulting cyclic compounds are cyclic hemiacetal.
Cyclic Forms of monosaccharides (Steps):
o Write
projection
formula
for
monosaccharide.
o All OH groups to the right, write them
BELOW the ring; all OH groups to the left,
write the ABOVE the ring.
o Write in a counterclockwise manner. C5 is
the attachment point of the C6.
o The final OH group will attach itself to the
carbonyl group. Two stereoisomers are
possible depending on the closure
If last OH is with the same side with
CH2OH, it is Beta.
If last OH is with the opposite side
with CH2OH, it is Alpha.
Both alpha and beta structures are
called as anomers. They only differ in
the positions of the substituents on
the anomeric (hemiacetal) carbon
atom.
Read
about
Cyclic
Forms
of
Other
Monosaccharides
HAWORTH PROJECTION FORMULAS
A two-dimensional structural notation that
specifies the three-dimensional structure of a
cyclic form of a monosaccharide.

o Position of the CH2OH in the ring determines

if the structure is D- or L-. (Above: D-; Below:
L-)
o Alpha or beta configuration is determined by
the position of the OH in carbon 1. (Same
side with CH2OH Beta; Opposite side with
CH2OH Alpha)
REACTIONS OF MONOSACCHARIDES
Five important reactions:
o Oxidation to acidic sugars
o Reduction of sugar alcohols
o Glycoside formation
o Phosphate ester formation
o Amino sugar formation
Oxidation to Produce Acidic Sugar
Remember that:
o Primary alcohol undergoing oxidation
Aldehyde
o Aldehyde undergoing oxidation Carboxylic
acid
o Aldehyde undergoing reduction Primary
alcohol
Can yield three different types of acidic sugars
depending on the oxidizing agents used.
o Weak oxidizing agents (Tollens and
Benedicts), oxidize the aldehyde end of an
aldose to give an aldonic acid. (Change
CHO end to COOH)
Example: Oxidation of glucose will
form gluconic acid.
o Aldoses are REDUCING SUGARS.
Tollens from Ag+ to Ag.
Benedicts from Cu2+ to Cu+

Stoker, H.S. (2016). General, Organic, and Biological Chemistry: Seventh Edition. Cengage:USA.

o Under basic conditions, ketoses are also

reduction sugars. In this condition, ketose
will first rearrange to become an aldose, the
aldose will be the one to react.
o Strong oxidizing agents can oxidize both
ends of a monosaccharide at the same time
(Change both CHO and CH2OH to COOH),
producing a dicarboxylic acid, known as
aldaric acids.
o In biochemical systems, enzymes can
oxidize the primary alcohol without the
oxidation of the aldehyde group (Change
only CH2OH to COOH).
Reduction to Produce Sugar Alcohols
The carbonyl group can be reduced to a hydroxyl
group, using a hydrogen as the reducing agent.
Products are called sugar alcohols or alditols
(Change CHO to CH2OH)
Glycoside Formation
Reaction of cyclic forms of monosaccharides with
alcohols under acidic conditions, to form
glycosides (Change OH in Carbon 1 to OCH 3, byproduct: H2O)
o Glycoside an acetal formed from a cyclic
monosaccharide by replacement of the
hemiacetal carbon OH with an OR group.
Glucose Glucoside
Hemiacetal + Alcohol Glycoside
Phosphate Ester Formation
Reaction with inorganic oxyacids to form inorganic
esters.

Phosphate esters are formed from phosphoric

acid.
Change the OH in carbon one to a phosphate
group
or
the
OH of the CH2OH to a phosphate group.

Amino Sugar Formation

Replacement of one of the hydroxyl groups with
an amino acid (Change one of the OH group
expect in carbon one, to a NH2)
Review Chemistry at Glance: Sugar Terminology
Associated with Monosaccharides and Their Derivatives

DISACCHARIDES
A carbohydrate in which two monosaccharides are
bonded together.
Formed by reaction a cyclic form of a
monosaccharide with an alcohol (as seen in
glycoside formation).
o Monosaccharide
will
function
as
a
hemiacetal while the other monosaccharide
will function as an alcohol, forming a
disaccharide, the glycoside.
The bond that links the two monosaccharides
together is called a glycosidic linkage.
o Glycosidic linkage the bond between two
monosaccharides resulting from the reaction
between the hemiacetal carbon atom OH
group of one monosaccharide and an OH
group on the other monosaccharide.
Maltose

Stoker, H.S. (2016). General, Organic, and Biological Chemistry: Seventh Edition. Cengage:USA.

Malt sugar (found in malt, which contains maltose)

Produced when a polysaccharide starch breaks
down.
Made up of two D-glucose units
o One must be an alpha-D-glucose
o Link is called an alpha-(1,4)-linkage because
the OH which are connected are from
Carbon 1 and Carbon 4.
Hydrolysis of Maltose in acidic condition or in a
maltase catalyst
o D-Maltose + H2O 2 D-glucose
o Maltase will break the alpha-(1,4)-linkage.

Cellobiose
Produced as an intermediate in the hydrolysis of
the polysaccharide cellulose.
Made up of two D-glucose units
o One must be a beta-D-glucose
o Link is called a beta-(1,4)-linkage because
the OH which are connected are from
Carbon 1 and Carbon 4.
Hydrolysis of cellobiose in acidic condition or in a
cellobiase catalyst
o D-Cellobiose + H2O 2 D-glucose
o Cellobiase will break the beta-(1,4)-linkage
Lactose
Milk sugar (found in milk)
Made up of a beta-D-galactose unit and any Dglucose unit
o Link is a beta-(1,4) glysosidic linkage
Formation of lactose in mammary glands
o Uptake of glucose in bloodstream.
o Glucose will under go epimerization to
yielding galactose, and then the beta-(1,4)

glysosidic linkage forms between the

glucose and galactose.
Souring of milk converts lactose to lactic acid.
o To retard the souring process, milk
undergoes pasteurization.
Hydrolysis of Lactose in acidic condition or in a
lactase catalyst
o D-Lactose + H2O D-galactose + D-glucose
o Lactase will break the beta-(1,4) glysosidic
linkage.

Sucrose
Table sugar
Most abundant disaccharides in the plant
kingdom.
Made up to alpha-D-glucose and beta-D-fructose
o Link is called an alpha, beta-(1-2) glycosidic
linkage. Link is formed in the carbon one of
glucose and carbon 2 of fructose.
Nonreducing sugar
Hydrolysis of Sucrose in acidic condition or in a
surcase catalyst
o D-Sucrose + H2O D-glucose + D-fructose
o Sucrase will break the alpha, beta-(1-2)
glycosidic linkage.
o Both D-glucose and D-fructose are invert
sugars.
Read about Other Types of Glycosidic Linkages

OLIGOSACCHARIDES
Carbohydrates that contain three to ten
monosaccharide units bonded to each other via
glycosidic linkages.
Human lacks digestive enzyme to break the
oligosaccharides,
hence
they
will
remain
undigested.
Stoker, H.S. (2016). General, Organic, and Biological Chemistry: Seventh Edition. Cengage:USA.
6

o When bacteria act upon them, it will

produce discomfort and flatulence.
Associated with the complex molecules of blood
chemistry

Read more about oligosaccharides.

GENERAL
CHARACTERISITCS
OF
POLYSACCHARIDES
Often called as glycans.
Important parameters to distinguish various
glycans:
o The identity of the monosaccharide
repeating unit/s in the polymer chain.
Homopolysaccharide one repeating
monosaccharide monomer is present
Heteropolysaccharide more than one
repeating monomer is present
o The length of the polymer chain.
Hundred monomer units to over
50,000 monomer units
o The type of glycosidic linkage between
monomer units.
o The degree of branching of the polymer
chain.
Proteins have branched-chains.
Nucleic acids have linear chains.
STORAGE POLYSACCHARIDES
A polysaccharide that is a storage form for
monosaccharides and is used as an energy source
in cells.

Homopolysaccharide containing only glucose

monosaccharide units.
Energy-storage polysaccharides in plants
o Excess glucose will be converted to starch
for later use
Two different polyglucose polysaccharides can be
isolated:
o Amylose

unbranched-chain
glucose
polymer
Linked
by
alpha-(1,4)
glycosidic
linkages
300-500 monomers are present
Stable in helical arrangement formed
by twisting the flexible glucose chain.
o Amylopectin branched glucose polymer
Branch occurs once every 25-30
glucose units
Linked
by
alpha-(1,4)
glycosidic
linkages in the linear part and alpha(1,6) glycosidic linkages in the
branched part
100,000 monomers may be present
Iodine test is carried out to test the presence of
starch in solution.
o (+): dark blue-black color.

Glycogen
A polysaccharide containing only glucose units.
Glucose storage polysaccharide in humans and
animals
Has the same function with that of the plants,
hence referred to as animal starch.
Linked by both alpha-(1,4) glycosidic linkages in
the linear part and alpha-(1,6) glycosidic linkages

Starch
Stoker, H.S. (2016). General, Organic, and Biological Chemistry: Seventh Edition. Cengage:USA.

Three times more branched than amylopectin with

up 1,000,000 glucose units present.
Excess glucose glycogen to be stored in liver
and muscle tissue
o Glucose to Glycogen is called Glycogenesis
o Glycogen
to
Glucose
is
called
Glycogenolysis

STRUCTURAL POLYSACCHARIDES
A polysaccharide that serves as a structural
element in plant cell walls and animal
exoskeletons
Two
of
the
most
important
structural
polysaccharides:
o Cellulose
and
Chitin,
both
homopolysaccharides
Cellulose
The structural component of plant cell walls, most
abundant naturally occurring polysaccharide.
Woody portion of plants
An unbranched glucose polymer
o Linked by beta-(1,4) glycosidic linkages
o Linear structure rather than spiral-like
structure in amylose
Water-insoluble due to linearity
Contains 5,000 glucose units.
o Cotton is 95% cellulose
Humans cannot digest cellulose because we lack
enzymes to break beta-(1,4) glycosidic linkages.
Chitin
Second most
polysaccharide.

abundant

naturally

occurring

Gives rigidity to the exoskeletons of crabs,

lobsters, shrimps, insects and other anthropods;
also, found in the cell walls of fungi.
The glucose present is a derivate, N-acetyl-Dglucosame (NAG).
Hydrolysis of chitin will form D-glucosamine.

ACIDIC POLYSACCHARIDES
A 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
sulfate group or a carboxyl group.
These are heteropolysaccharides.
o Two different monosaccharides are present
in an alternating pattern.
Hyaluronic Acid
Contains alternating residues of N-aceytl-beta-Dglucosamine (NAG) and D-glucuronate.
o D-glucuronate is formed when D-glucoronic
aid loses its acidic hydrogen atom.
Product obtained when the CH2OH
group of a glucose is oxidized to a
COOH group
Linked by alternating beta-(1,3) and beta-(1,4)
glycosidic linkages.
Heparin
A small highly sulfated polysaccharide with only
15-90 disaccharide residues per chain.
Monosaccharides
present
in
heparin;s
disaccharide repeaing unit are a sulfate dericatice
of D-gluuronate and a doubly sulfated derivative
of D-glucosamine. Both of these monosaccharide

Stoker, H.S. (2016). General, Organic, and Biological Chemistry: Seventh Edition. Cengage:USA.

derivatives contain two negatively charged acidic

groups.
A blood anticoagulant.

Read about Dietary Considerations and Carbohydrates.

Read about Glycolipids and Glycoproteins: Cell
Recognition

Stoker, H.S. (2016). General, Organic, and Biological Chemistry: Seventh Edition. Cengage:USA.