BIOCHEMISTRY

Biochemistry - Lecture | By KMAE & MTP

BSN-1E | PROF. John Michael M. Lico | FINALS-SEM 1 2022

○ commonly found in
conjugated biomolecules
CARBOHYDRATES
● Polysaccharide
● Most Abundant Biomolecules ○ hundreds to 50,000 units
● Composed of C, O, H, According ■ glycogen, starch,
to the formula (C•H2O)n or 𝐶𝑛𝐻2𝑛𝑂𝑛 cellulose
where n > 3
● Polyhydroxy aldehyde or Monosaccharides
polyhydroxy ketone Classified by:
● Basic carbohydrate units are (A) Number of carbon atoms
monosaccharides Name Formula
● Polymers of monosaccharides
units are are called Triose C3H6O3
polysaccharides
Tetrose C4H8O4
FUNCTIONS
● Provide Energy
Pentose C5H10O5
● Precursor of other biomolecules
● Storage-energy reserve
● Part of Nucleic Acid Structure Hexose C6H12O6
● Component of Cell membrane
(with lipids)
Heptose C7H14O7
CLASSIFICATION
● Monosaccharide Octose C8H16O8
○ smallest and the building
block
○ contains only one unit of
polyhydroxy aldehyde or
polyhydroxy ketone
○ cannot be broken down into
simpler units
○ soluble in water
■ glucose, galactose,
fructose
● Disaccharide
○ two monosaccharides ● D-configuration
bonded by glycosidic bond ○ Dextrorotatory
○ soluble in water ○ existing sugars in nature
■ sucrose, lactose, ○ -OH or hydroxyl group is
maltose found in the right side of the
● Oligosaccharide fischer projection
○ three to nine ● L-configuration
monosaccharides that are ○ Levorotatory
covalently bonded to each ○ -OH is found in the left side
other

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BIOCHEMISTRY
Biochemistry - Lecture | By KMAE & MTP
BSN-1E | PROF. John Michael M. Lico | FINALS-SEM 1 2022

(B) Functional Group ● An achiral molecule is a molecule

aldose: contains an aldehyde group whose mirror images are
ketose: contains a ketone group superimposable
○ No handedness = achiral =
superimposable (non mirror
images)
○ Achiral molecules do not
possess handedness
● 2^n where n is the number or
chiral centers

STEREOISOMERISM OF
MONOSACCHARIDES
Stereoisomers are isomers that have the
same molecular and structural formulas
but differ in the orientation of atoms in
space.

● According to the conventions

proposed by Fischer
○ D-monosaccharide
■ Monosaccharide
CHIRALITY: HANDEDNESS IN that, when written
MOLECULES as a Fischer
● Most biological molecules, projection, has the
including carbohydrates, exhibit -OH on its
the property of “handedness” penultimate carbon
● Most monosaccharides exist in two on the right
forms: ○ L-monosaccharide
○ Left (L) Handed ■ Monosaccharide
○ Right (D) Handed that, when written
These forms are related in the as a Fischer
same way as two hands that are projection, has the
“mirror images” of each other -OH on its
penultimate carbon
CHIRALITY on the left
● A trisubstituted methane molecule
such as bronchial iodomethane, is ● Penultimate Carbon - Second to
the simplest example of an chiral the last Carbon in the chain of the
organic molecule Fischer Projection
● Any chiral carbon with four diff
groups possess:
○ Handedness = chiral =
nonsuperimposable (mirror
images)

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BIOCHEMISTRY
Biochemistry - Lecture | By KMAE & MTP
BSN-1E | PROF. John Michael M. Lico | FINALS-SEM 1 2022

STEREOISOMERS: ENANTIOMERS AND CYCLIC CARBOHYDRATES

DIASTEREOMERS ● Monosaccharides have -OH and
● Enantiomers: C=O groups in the same molecule
○ stereoisomers that are and exist almost entirely as five-
mirror images/ and six-membered rings
nonsuperimposable ● anomeric carbon: the new
○ always come in pairs stereocenter resulting from cyclic
○ all of the chiral Carbons formation
change configuration ● anomers: carbohydrates that differ
○ example: D-glucose and in configuration only at their
L-glucose are enantiomers anomeric carbons
● Diastereomers: ● The two anomers can freely
○ stereoisomers that are not interconvert in solution -
mirror images mutarotation
○ at least two chiral Carbons
that did not change HAWORTH PROJECTIONS
configuration ● Common way of writing a structural
○ example: D-ribose and formula to represent the cyclic
D-xylose are structure of monosaccharides with
diastereomers a simple three-dimensional
● Epimers: perspective.
○ diastereomers that differ ○ Left side of Fischer
around 1 carbon projection = lower part of
○ example: D-glucose and the ring
D-galactose are epimers ○ Right side of Fischer
projection = upper part of
FISCHER PROJECTION the ring
● A two-dimensional representation ● Pyranose - 6-membered ring;
for showing the configuration of aldoses
tetrahedral stereocenters ● Furanose - 5-membered ring;
○ “fishbone” ketoses
○ skeletal formation of sugar
● By convention, horizontal lines
represent bonds projecting from
the plane of the paper toward the
viewer, and vertical lines represent
bonds projecting away from the
viewer.

β-D-glucose
- beta D-glucose
- formation of -OH can be seen in
the upper portion of the ring

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BIOCHEMISTRY
Biochemistry - Lecture | By KMAE & MTP
BSN-1E | PROF. John Michael M. Lico | FINALS-SEM 1 2022

α-D-glucose REACTIONS OF MONOSACCHARIDES

- alpha D-glucose 5 Important Reactions of
- formation of -OH can be seen in Monosaccharides:
the lower portion of the ring Oxidation —> Acidic Sugars
Reduction —> Sugar Alcohols
COMMON MONOSACCHARIDES Glycoside Formation
Phosphate Ester Formation
GLUCOSE Amino Sugar Formation
● Also called dextrose (D-glucose)
and blood sugar
● Found in large quantities
throughout the living world
● Primary fuel for living cells These reactions will be considered with
● Preferred energy source of brain respect to glucose; other aldoses, as well
cells & cells that have few or no as ketoses, undergo similar reactions.
mitochondria
● Large amounts generate energy in ● Oxidation
cells that have limited oxygen ○ Gives three different types
supply (eyeball) of acidic sugars depending
● Its dietary sources include starch & of the type of oxidizing
disaccharides, lactose, maltose, agent used:
and sucrose ■ Weak oxidizing
agents like Tollens
GALACTOSE and Benedict’s
● Necessary to synthesize lactose, Solutions oxidize
glycolipids, certain phospholipids, the aldehyde end to
proteoglycans, and glycoproteins. give an aldonic
● Readily synthesized from reaction. (Aldonic
glucose-1-phosphate. acid)
■ Strong oxidizing
FRUCTOSE agents like nitric
● also called levulose or fruit sugar acid can oxidize
● Found in some vegetables and in both ends of a
honey monosaccharide at
● The sweetest sugar, twice as the same time to
sweet as sucrose produce aldaric
● Sweetening agent in processed acid. (Aldaric acid)
food products ■ In biochemical
● Large amounts are used in the systems, enzymes
male reproductive tract can oxidize the
(synthesized in the seminal primary alcohol end
vesicles and then incorporated into of an aldose such
semen, the sperm use fructose as as glucose, without
an energy source) oxidation of the
aldehyde group, to
produce an

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BIOCHEMISTRY
Biochemistry - Lecture | By KMAE & MTP
BSN-1E | PROF. John Michael M. Lico | FINALS-SEM 1 2022

alduronic acid. The sugars are oxidized to carboxylic acid

(Alduronic acid)
● Reduction
○ The carbonyl group in a
monosaccharide (either an
aldose or a ketose) is
reduced to a hydroxyl
group using hydrogen as
the reducing agent.
○ Product is the
corresponding polyhydroxy
alcohol, sugar alcohol.
○ e.g., sorbitol (glucitol)- used
as moisturizing agents in
foods and cosmetics and
as a sweetening agent in
chewing gum.
○ major factor in the
formation of cataracts due
to diabetes
○ Under prescribed
conditions, some sugars
reduce silver ions to free
silver and copper (II) ions to
copper (I) ions. Such
sugars are called reducing
sugars.
○ A reducing sugar will have
one of the following groups:
an aldehyde group
(glyceraldehyde), a group.
hydroxyketone group
(fructose), a cyclic
hemiacetal group (glucose
and maltose).
The Benedict, Barfoed, and
Fehling Tests are based on the formation
of a brick red copper (I) oxide precipitate
as a positive result while the Tollen’s Test
is based on the formation of a silver mirror.
The Barfoed Test is more sensitive
that it can distinguish a reducing
monosaccharide from a reducing
disaccharide.
and the metal ions are reduced.
● Glycoside Formation
○ The cyclic forms of
monosaccharides, the
hemiacetals, react with
alcohols to form acetals,
also called glycosides
○ A glycoside is an acetal
formed from a cyclic
monosaccharide by
replacement of the
hemiacetal carbon-OH
group with an-OR group to
form a double ether
● Phosphate Ester Formation
○ The hydroxyl groups of a
monosaccharide can react
with inorganic oxyacids to
form inorganic esters.
○ Phosphate esters of
various monosaccharides
are stable in aqueous
solution and play important
roles in the metabolism of
carbohydrates.
● Amino Sugar Formation
○ One of the Hydroxyl group
of a monosaccharide is
replaced with an amino
○ In naturally occurring amino
sugars the carbon 2
hydroxyl group is
replaced by an amino
group.
○ Amino sugars and their
N-acetyl derivatives are
important building blocks of
polysaccharides such as
chitin and hyaluronic acid.

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BIOCHEMISTRY
Biochemistry - Lecture | By KMAE & MTP
BSN-1E | PROF. John Michael M. Lico | FINALS-SEM 1 2022

GLYCOSIDIC BOND through glycosidic bond between

● Glycoside: a carbohydrate in
which the –OH of the anomeric
carbon is replaced by –OR
○ those derived from
furanoses are furanosides;
those derived from
pyranoses are
pyranosides
○ glycosidic bond: the bond
from the anomeric carbon
to the -OR group
both anomeric carbons.
● A nonreducing sugar.
OLIGOSACCHARIDES
● Carbohydrates that contain three
to nine monosaccharides
● Arrangement of these
monosaccharide in the
oligosaccharide determines the
blood type of a person.

DISACCHARIDES

MALTOSE
● Also called malt sugar
● An intermediate product of starch
hydrolysis.
● A disaccharide with an α(1,4)
glycosidic linkage between two
D-glucose molecules.

CELLOBIOSE
● A degradation product of cellulose
● Contains 2 molecules of glucose POLYSACCHARIDES
linked by a β(1,4) glycosidic ● Storage Polysaccharide
bond ● Starch is the principal food reserve
in plants - polymers of α-D-
LACTOSE glucose units
● Also called as milk sugar
● A disaccharide composed of one
molecule of galactose linked
through the OH group on C1 in a
β-glycosidic linkage to the OH of
C4 of a molecule of glucose

SUCROSE
● Commonly called table sugar,
cane sugar, and beet sugar.
● Produced in the leaves and stems
of plants.
● Contain both α,D-glucose and
β,D-fructose residues linked

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BIOCHEMISTRY
Biochemistry - Lecture | By KMAE & MTP
BSN-1E | PROF. John Michael M. Lico | FINALS-SEM 1 2022

GLYCOGEN IMPORTANT INFO

● Glycogen is the storage
polysaccharide in animals
○ bush-like with α(1→6)
branch points
○ Every 8 - 12 glucose
residues for glycogen
● only monosaccharides with 3-7
carbon atoms are commonly
found in nature
● Latin word for sugar is
“saccharum”

STRUCTURAL POLYSACCHARIDE
CELLULOSE
● A polysaccharide composed of
D-glucopyranose residues linked
by β(1,4)-glycosidic bonds
● The most important structural
polysaccharide of plants
● Comprises one-third of plant
biomass, hence it is the most
abundant organic substance on
earth
● Not digested by human beings but
can be digested by some animal
species using the enzyme
cellulase

CHITIN
● A polysaccharide that is like
cellulose, both in its biological
function and its primary,
secondary, and tertiary structure.
● Chitin is present in the cell walls of
fungi and is the fundamental
material in the exoskeletons of
crustaceans, insects, and spiders.
● The structure of chitin, an
extended ribbon, is identical to
cellulose, except that the -OH
group on each C-2 is replaced by
− 𝑁𝐻𝐶𝑂𝐶𝐻3, so that the repeating
units are N-acetyl-D-glucosamines
in β(1,4) linkage.

CHITOSAN
● made by treating the chitin shells
of shrimp and other crustaceans
with an alkaline substance.

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BIOCHEMISTRY
Biochemistry - Lecture | By KMAE & MTP
BSN-1E | PROF. John Michael M. Lico | FINALS-SEM 1 2022

Monosaccharide
- Tri = Three carbon units
- Classify base on the Number of
Carbons
- Carbohydrates in Dextro Blah Blah
- D Monomer Units
- Because the OH is found in
the Right/Base Line
- Classify base on the functional
group
- Aldose = Sugar molecule
contains aldehyde
functional group
- C=H
- Aldose = Aldotriose
- Ketose

Aldoses
- Carbon = 1

Ketoses
- Carbon = 2

Chirality
- Both are need to determine the
number of carbons