CARBOHYDRATES

compound that consists only of Carbon,

Hydrogen and Oxygen
Saccharide which comes from the Greek
word skkharon, meaning "sugar"
most abundant biomolecules on earth
Divided into Monosaccharides,
Disaccharides, Polysaccharides and
Oligosaccharides
Widely distributed in plants and animals
Glucose is the most important
carbohydrate

Major metabolic fuel of mammals and

universal fuel of the fetus
Oxidation of carbohydrates as a source of
energy
Structural and protective elements in the
connective tissue of animals
Participate in recognition and adhesion of cells
Determine the metabolic fate of proteins and
lipids when attached to them
Structural elements of nucleic acids and
coenzymes

Consists of the elements Carbon, Oxygen

and Hydrogen
Formula Cn(H2O)n
The structure of can be represented in
three ways:

Straight Chain
Cyclic Structure; Haworth Projection

Chair form

Outside of the body, glucose exists in its

straight chain form.
In this form, the carbon atoms are
bound together in a long chain, with the
hydrogen and oxygen atoms bound at
either end and along the sides.

Within a living organism -humans, plants, or animals -glucose exists in a ring that
resembles a hexagon

This cyclic structure is

favored on thermodynamic
ground

These two forms often coexist

rings can open and re-close
Anomeric carbon- carbon about which
rotation occurs
two forms are termed Anomers

Furanose and Pyranose forms exist in

equilibrium with the straight-chain form.
Two conformations

chair form and the boat form. chair form is

more stable

Constituents of the ring

project above or below the plane- axial
project parallel to the plane- equatorial.

Monosaccharides - cannot be
hydrolyzed into simpler carbohydrates
According to number of Carbon atoms
Trioses
Tetroses
Pentoses
Hexoses
Heptoses
Nonoses

Lippincot Biochemistry, 3rd ed.

Monosaccharides - cannot be
hydrolyzed into simpler carbohydrates
According to functional group attached
Aldose
Ketose
Polyhydric alcohols/
Sugar alcohols/ Polyols

Lippincot Biochemistry, 3rd ed.

Disaccharides - condensation

products of two monosaccharide units

eg. Maltose (glu+glu), sucrose (glu+fru)

Oligosaccharides - condensation
products of three to ten
monosaccharides
-Most are undigested by human
enzymes

 Polysaccharides - condensation products

of more than ten monosaccharide units

According
to
identity
monosaccharides

of

constituent

Hexosans
Pentosans

eg. starches, dextrins (linear/branched polymers)

Nonstarch polysaccharides not digested by human
enzymes
- major component of dietary fiber
- eg. cellulose (plant cell wall, glucose polymer);
inulin(storage carbohydrate in some plants, fructose
polymer)

Triose
Tetrose
No. of
Carbon
atoms
Monosaccharides

Hexose
Heptose

Functional
group
attachment
CARBOHYDRATE

Pentose

Aldose

Ketose

Disaccharides

Oligosaccharides
Hexosan

Identity of
constituent
monosaccharides
Classification accg. to Harpers Illustrated Biochemistry, 28th ed.
Polysaccharides

Pentosan

Isomers are compounds with the

same
molecular
formula
but
different chemical structures.
Isomers do not necessarily share similar
properties, unless they also have the
same functional groups.
There are 2 main forms of Isomerism:
Structural Isomerism and Stereoisomerism.

In structural isomers, sometimes referred

to as constitutional isomers, the atoms
and functional groups are joined
together in different ways.
Differ in the order in which the atoms are
connected.
Structural
isomers
have
different IUPAC names and may or may
not belong to the same functional
group.

Stereoisomers
are
isomeric
molecules
that
have
the
same
molecular formula and sequence of
bonded atoms (constitution), but that
differ only in the three-dimensional
orientations of their atoms in space.
Number of possible isomers depends on
(n), number of asymmetric carbon
atoms, = 2 .

Can be interconverted exclusively by

rotations about formally single bonds
Interconversion
necessarily
involves
breaking and reforming of chemical
bonds

Rotamers
Specific type of conformational isomers
When the rotation leading to different

conformations is restricted (hindered)

rotation
There exists a rotational energy barrier that
needs to be overcome to convert one
conformer to another

Stereoisomers that do not readily

interconvert at room temperature and
can be separated.
Geometric and Optical

Geometric
Configurational isomers that differ in the

spatial position around a bond with

restricted rotation (e.g. a double bond)
Cis-trans and E-Z Conformation

Cis-trans
in which cis means "on the same side"
Trans means "on the other side" or "across".
not effective when there are more than two

different substituents on a double bond

E-Z
E isomer:
If the two groups of higher priority are on
opposite sides of the double bond
(from entgegen the German word for
"opposite").
Z isomer:
If the two groups of higher priority are on the
same side of the double bond
(from zusammen, the German word for
"together").

E-Z

Configurational isomers that differ in the

3D relationship of the substituents about
one or more atoms.
Divided into:

Enantiomers
non-superimposable mirror images
Diastereomers
Not enantiomers

Have identical chemical and physical

properties
Except for their ability to rotate planepolarized light (+/) by equal amounts but
in opposite directions
Racemic mixture

A mixture of equal parts of an optically active

isomer and its enantiomer

has zero net rotation of plane-polarized
light because the positive rotation of each (+)
form is exactly counteracted by the negative
rotation of a () one.

R- and S If the center is oriented so that the lowestpriority of the four is pointed away from a
viewer, two possibilities:

If the priority of the remaining three

substituents decreases in clockwise direction, it

is labeled R (for Rectus, Latin for right),
if it decreases in counterclockwise direction, it
is S (for Sinister, Latin for left).

By optical activity: (+)- and ()- or d- and l direction in which it rotates the plane of polarized

light
(+) or d: rotates the light clockwise, dextrorotatory
(-) or l: rotates light counterclockwise, levorotatory

By configuration: D- and L by the spatial configuration of its atoms by

relating the molecule to glyceraldehyde

COOH R NH2 H,
D: groups are arranged clockwise around the
carbon atom
L: groups are arranged counterclockwise around
the carbon atom

Two or more stereoisomers of a compound

have different configurations at one or
more (but not all) of the equivalent
(related) stereocenters
stereocenter: atom that bears groups such

that an interchanging of any two groups leads

to a stereoisomer

Are not mirror images of each other

Epimers: diastereoisomers differ from each
other at only one stereocenter

Threo
2 identical

substituents on the
opposite side

Erythro
2 identical

substituents on the
same side

Asymmetric Carbon
carbon atom that is attached to four different

types of atom or four different groups of atoms

Optical Activity or Optical Rotation

turning of the plane of linearly polarized light

about the direction of motion as the light travels

through certain materials

Reference Sugar
Glyerose or glyceraldehyde
Parent compound of the carbohydrate family
Basis for D and L isomerism

Epimers
are diastereomers that differ in configuration

of only one stereogenic center

Anomers
also called anomeric carbons
special type of epimer
It is one of two stereoisomers of a cyclic

saccharide that differs only in its

configuration at the hemiacetal or hemiketal
carbon

Change in the optical rotation that occurs

by epimerization (that is the change in the
equilibrium between two epimers, when
the
corresponding stereocenters interconvert)
Cyclic sugars show mutarotation as and
anomeric forms interconvert
The optical rotation of the solution
depends on the optical rotation of each
anomer and their ratio in the solution.

Determined by its spatial relationship to

glycerose (glyceraldehyde)
Orientation of H and OH groups around
the carbon atom adjacent to the
terminal primary alcohol carbon

D isomer : OH on the right side

L isomer: OH on the left side

Most monosaccharides in mammals are

in D form

Presence of asymmetric carbon atoms

confers optical activity on the compound
Dextrorotatory or (+): light rotated to the right
Levorotatory or (-): light rotated to the left

A compound may be designated D(-),

D(+), L(-) or L(+),
Naturally occurring form of fructose is D(-)
Racemic mixture equal amounts of D and
L isomers, no optical activity

Based on the fact that the stable ring

structures of monosaccharides are similar
to the ring structures of either pyran or
furan
Ketoses may also show ring formation
(fructofuranose and fructopyranose)
More than 99% of glucose is in the
pyranose form

Ring structure of aldose is hemiacetal

(formed by aldehyde and alcohol)
Ring structure of ketose is hemiketal (ketone
and alcohol)
Crystalline glucose is -D-glucopyranose
In solution: -glucopyranose (38%), glucopyranose (62%)
Equilibriation is accompanied by optical
rotation as the hemiacetal ring opens and
reforms with the change of H and OH on C1

The optical rotation of glucose in solution is

dextrorotatory, hence the name dextrose.

Result in variations in configurations of

the OH and H on Carbon 2,3,4 of
glucose
Most important epimers of glucose are

Mannose (epimerization at carbon 2)

Galactose (epimerization at carbon 4)

Fructose and glucose

Same molecular formula differs in structure

Potential keto group in position 2 of

fructose
Potential aldehyde group in position 2 of
glucose

Sugars may be represented by the

formula CnH2nO
Acyclic mono and disaccharides
contain aldehyde groups or ketone
groups
These groups contain C=O where one
may find its reactivity

Saccharides with a ring greater than one

in their structure is formation from two or
more monosaccharieds joined by a
bond called glycosidic bonds. This results
a to a loss of a molecule of water per
bond.

Carbohydrates that cannot be

hydrolyzed into simpler carbohydrates
May be classified as trioses, tetroses,
pentoses, hexoses, heptoses (# of C
atoms)
May be classified as aldose (aldehyde
group) or ketose (ketone group)

Two of the most common

monosaccharides are glucose and
fructose. Both glucose and fructose have
the same chemical formula (C6H12O6);
however, they have different structures,
as shown.

Glucose is the primary form of sugar

stored in the human body for energy.
Fructose is the main sugar found in most
fruits.

Glucose is the most important carbohydrate

Dietary sugar absorbed in the bloodstream

Other sugars converted to glucose in the liver
Major metabolic fuel in mammals
Precursor for synthesis of all other
carbohydrates in the body
Glycogen for storage
Ribose and deoxyribose in nucleic acids
Galactose in lactose of milk

Glycolipids
Glycoproteins and Proteoglycans

DISACCHARIDES
Sugars formed by linking 2
mono-saccharide units by
glycosidic bond
Formed by dehydration
synthesis

DISACCHARIDES

SUCROSE
COMPOSITION O-- glucopyranosyl- (1-->2)-- Dfructofuranoside
STRUCTURE

SOURCE

Cane and beet sugar, sorghum and some fruits

and veg

Rare genetic lack of sucrase leads to sucrose

CLINICAL
SIGNIFICANCE intolerancediarrhea and flatulence

MALTOSE
COMPOSITION

O--glucopyranosyl- (1-->4)--D-glucopyranose

STRUCTURE

SOURCE
CLINICAL
SIGNIFICANCE

Enzymic hydrolysis of starch (amylase)

Germinating cereals and malt

LACTOSE

COMPOSITION O-- galactopyranosyl- (1-->4)--Dglucopyranose

STRUCTURE

SOURCE

Milk (and many pharmaceutical preparations as

filler)

Lack of lactase (alactasia) leads to lactose

CLINICAL
SIGNIFICANCE intolerancediarrhea and flatulence
May be excreted in the urine in pregnancy

polymers made up of many

monosaccharides joined together by
glycosidic bonds by condensation
reaction

Based on Structure:
1. homo-polysaccharide - only one type
of monosaccharide repeating in the
chain

2. hetero-polysaccharide - composed of
two or more types of monosaccharides

Based on Function
1.Structural cellulose, chitin
2. Storage energy sources:
glycogen, starch

Chief constituent of plant cell walls

linear chain of several hundred to over ten
thousand (14) linked D-glucopyranose
units

multiple hydrogen bonds is responsible for

the high tensile strength or rigidity

a long-chain polymer of a N-acetylglucosamine (a derivative of glucose )

linked by (14) glycosidic bonds
component exoskeletons of arthropods
such as crustaceans and insects

chain of D-glucopyranose residues in

a (14) bond with branching by
(16) bond
synthesized from monomers of UDPglucose by the enzyme glycogen
synthase

amylo (14) to (16)

transglycosylase
- glycogen-branching enzyme

Reducing end attached to glycogenin

Glucose residue linked by -1,6

Nonreducing ends
Glucose residue linked by -1,4

occurs mainly in the cytosol of liver cells and

muscles.
Requires:
primer already existing short chains of glucose
Initiator Glycogenin ( a protein with tyrosine
residue which serve as site at which initial glucose
unit is attached)
- required when the glycogen stores are
depleted
UDP-Glu units (Uridine diphosphate glucose units).
Two enzymes:

Glycogen synthase
Branching enzyme

4 Steps:
Synthesis of UDP-glucose
Synthesis of a primer to initiate glycogen
synthesis
Elongation of glycogen chains by
glycogen synthase
Formation of branches in glycogen

Glucose + ATP

Glucose 6- P

Glucokinase (liver)

Glucose 6- P + ADP

Hexokinase (peripheral tissue)

Phosphoglucomutase

Glucose 1- P + UTP

UDP- Glucose
pyrophosphorylase

Glucose 1- P

UDP-glucose + PPi

Glycogenin
UDP Glu
UDP

Primer
UDP Glu

R
Glycogen synthase

UDP

Elongated
branch
of glycogen

R
Branching enzyme

Formation of
new branches

stored in the liver and muscles

main form of stored carbohydrate in the body

ENZYME
Glycogen
formation

Glycogen
synthase

Glycogen
breakdown

Glycogen
phosphorylase

HORMONE
insulin
glucagon

insulin

hypoglycemia glycogen
accumulation

insulin

diabetes

glycogen
depletion

glycogen storage diseases - inborn errors

of metabolism are caused by deficiencies
of enzymes necessary for glycogen synthesis
or breakdown (ex. von Gierke's Disease (type IA) glucose-6phosphatase deficiency)

Liver maintains blood glucose

concentration at normal levels
Skeletal muscle fuel reserve for ATP
synthesis needed for muscle contraction

Homopolymer of glucose forming a

glucosidic chain (glucosan/glucan)
Linear Amylose (13-20%) and branched
Amylopectin (80-85%)
Branched chains of 24-30 glucose
residues united by (14) bonds with
branching by (16) bonds

Broken down by amylase ( from saliva

and pancreas)
Amylose
maltose & Maltotriose
Amylopectin
glucose & dextrin
Dissacharidases( ex. Maltase) enzymes
present in intestinal villi; breakdown of
disaccharides into monosaccharides (ex.
Glucose)

Found in naturally occurring

polysaccharides produced by many types
of plants that use it as a means of storing
energy; found in roots or rhizomes
polymers composed mainly of fructose units
joined by a (21) glycosidic bond
used clinically as a highly accurate
measure of glomerular filtration rate (the
flow rate of filtered fluid through the kidney)
it is completely filtered at the glomerulus
but neither secreted nor reabsorbed by the
tubules

low-molecular-weight carbohydrates
produced by the hydrolysis of starch
polymers of D-glucose units linked by (1,4) or -(1,6) glycosidic bonds.
Inulin and dextrin are water soluble and
indigestible dietary fiber (prebiotics) that
stimulate the growth and activity of
bacteria in the digestive system which
are beneficial to the health of the body

Chitin

N-acetyl-D-glucosamine units joined by b1-4 glycosidic bonds

derivative of glucose
Main component of the cell walls of
fungi, exoskeletons of crustaceans and
arthropods etc.
May be compared to the
polysaccharide Cellulose (substitute the
hydroxyl group on each monomer with
an acetyl amine group) and the protein
Keratin (similar structural functions)

Agriculture

a good inducer for defense mechanisms in plants. It was

recently tested as a fertilizer that can help plants develop
healthy immune responses, and have a much better yield and
life expectancy. Chitosan is derived from chitin.

Industrial

used as an additive to thicken and stabilize foods and

pharmaceuticals. It also acts as a binder in dyes, fabrics, and
adhesives. Industrial separation membranes and ionexchange resins can be made from chitin. Processes to size
and strengthen paper employ chitin

Medicine

Chitin's properties as a flexible and strong material make it

favorable as surgical thread. Its biodegradibility means it
wears away with time as the wound heals. Moreover, chitin
has some unusual properties that accelerate healing of
wounds in humans.
Occupations associated with high environmental chitin levels,
such as shellfish processors, are prone to high incidences of
asthma. Recent studies have suggested that chitin may play a
role in a possible pathway in human allergic disease.

A linear polysaccharide commercially

produced from the deacetylation of chitin
Used as a Biocontrol elicitor
Has water filtration uses
May be used industrially for car paints
Used as a hemostatic agent in bandages
Sold in tablet form at health stores as a fat binder
Studies have shown that chitosan is a soluble
dietary fiber and alters bile acid composition by
increasing the excretion of sterols and reducing
digestibility of ileal fats

 Also

called mucopolysaccharides
Comples carbohydrates containing
amino sugars and uronic acids
Attaches to a protein molecule to form a
proteoglycan which provide the ground
substance of connective tissues
Examples of proteoglycans are
hyaluronic acid, chondroitin sulfate and
heparin

The synthesis of the core proteins occurs in

the ER but most of the synthesis of gag
chains occur in the golgi apparatus
3 major events

Attachment to core proteins

Chain elongation
One enzyme, one linkage relationshio among
nucleotide sugars and glycoslytransferases

Chain termination
Results from sulfation and progression of the growing
GAG chain away from the membrane site of catalysis

Polymer of disaccharides
Promoter for early inflammation and moderates
the inflammatory response
Helps in tissue repair
Molecules that interact with HA has a role in
cancer metastasis (can therefore be used as a
tumor marker)
Medical applications includes use in eye
surgeries, treatment for osteoarthritis (also has
application in racing horses)and atopic
dermatitis
Used in skin care products

 Chain

of alternating sugars
Usually found in proteins as part of a
proteoglycan
An important structural component of
cartilage and provides much of its
resistance to compression
Used as an ingredient of an alternative
medicine to treat osteoarthritis

Widely used as an injectable coagulant

Does not directly break down clots but
prevents them from forming
Used medically to prevent deep vein
thrombosis, pulmonary embolism
Widely used in surgeries (e.g coronary bypass for heart

surgery)

Adverse reaction may cause heparin induced

thrombocytopenia

Both Keratan sulfate I and dermatan sulfate

are present in the cornea and presents a
critical role in corneal transparency

Dermatan sulfate may play an important role in

the development of atherosclerotic plaque
since arterial smooth muscle cells synthesize
these GAGs

Heparan sulfate is associated with the plasma

membrane of cells, with its core protein
spanning the membrane, acting as receptors
and may also participate in cell growth and
cell-cell commuication

Contains oligosaccharide chains covalently

attached to polypeptide chains
Occurs in most organisms, from bacteria to
humans and even viruses (where they play
key roles such as attachment to cells)
Almost all the plasma proteins in humans
(except albumin) are glycoproteins
Certain oligosaccharide chains encode
biologic information thus it is of great
physiologic value to decipher the so called
sugar code of life which is one of the
principal aims of glycobiology and
glycomics (study of glycomes)

Glycoproteins
Structural molecule

Collagen

Lubricant and
protective agent

Mucin

Transport molecule

Transferrin, ceruloplasmin

Immunologic
molecule

Immunoglobulins,
histocompatability

Hormone

Chorionic Gonadotropin,
tyroid stimulating
hormone(TSH)

Enzyme

Various, e.g, alkaline

phosphatase

Cell attachment
recognition site

Various proteins involved in cellcell(eg sperm-oocyte), virus-cell,

bacterium-cell, and hormone-cell
interactions

Antifreeze

Certain plasma proteins of coldwater fish

Interact with specific

carbohydrates

Lectins, Selectins (cell adhesion

lectins), antibodies

Receptor

Various proteins involved in

hormone and drug action
Calnexin, Calreticulin

Affect folding of
certain proteins
Regulation of
development

Notch and its analogs, key proteins

in development

Hemostasis (and
thrombosis)

Specific glycoproteins on the

surface membranes of platelets

Modulate physiochemical properties, eg

solubility, viscosity, charge, conformation,
denaturation, and binding sites for various
molecules, bacteria, viruses, and some
parasites
Protect against proteolysis, from inside and
outside of cell
Affect proteolytic processing of precursor
proteins to smaller products
Are involved in biologic activity, eg, of hCG
Affect insertion into membranes, intracellular
migration, sorting and secretion
May affect sites of metastases selected by
cancer cells

O-glycosidic
linkage

N-glycosidic
linkage

Glycosylphospha
tidylinosolanchored(GPIlinked)
Involving the
Involving the
Linked to the
hydroxyl side
amide nitrogen of carboxyl terminal
chain of serine or asparagine and amino acid of a
threonine and a Nprotein joined to
sugar such as N- acetylglucosamin an
acetylgalactosam e
oligosaccharide
ine eg, Mucin
(glycan)

The biosynthesis of N-linked glycoproteins

2 stages:

Assembly of Dol-P-P-oligosaccharide and transfer of

oligosaccharide
Processing of the oligosaccharide chain

Is important since the most readily accessible

glycoproteins (eg. Plasma proteins) mainly belong
to this group
The process itself has physiologic significance

administration of recombinant erythropoeitin to stimulate

erythropoiesis in patients with anemia

Correlation of different glycosyl transferases in various
types of cancer cells

Produced by epithelial tissues

Has a key characteristic ability to form gels,
and therefore forms functions from signaling
to forming chemical barriers
Some mucins are associated with controlling
mineralization,
including bone formation in
vertebrates
Overexpression of mucin proteins
is associated with many types of cancer

Mature mucins are composed of two distinct regions:

The amino- and carboxy-terminal regions are very lightly
glycosylated, but rich in cysteines. The cysteine residues
participate in establishing disulfide linkages within and
among mucin monomers
A large central region formed of multiple tandem repeats of
10 to 80 residue sequences in which up to half of the amino
acids are serine or threonine. This area becomes saturated
with hundreds of O-linked oligosaccharides. N-linked
oligosaccharides are also found on mucins, but in less
abundance than O-linked sugars

Is a generic term for the N- or O-substituted derivatives of

neuraminic acid, a monosaccharide with a nine-carbon
backbone
A constituent of both glycoproteins and gangliosides
Found widely distributed in animal tissues and to a lesser
extent in other species such as plants and bacteria
Metastatic cancer cells often express a high density of
sialic acid-rich glycoproteins. This helps these late-stage
cancer cells enter the blood stream. Sialic acid-rich
regions contribute to creating a negative charge on the
cells' surface. Since water is a polar molecule with partial
positive charges on both hydrogen atoms, it is attracted
to cell surfaces and membranes. This also contributes to
cellular fluid uptake.

Carbs against Cardio: More Evidence that

Refined Carbohydrates, not Fats, Threaten the
Heart
Processed carbohydrates may increase the risk of

obesity, diabetes and heart disease more than fat

does
a meta-analysiswhich combines data from several
studies found no association between the amount of
saturated fat consumed and the risk of heart disease.
do not merely suggest that saturated fats are not so
bad; they indicate that carbohydrates could be
worse.
Study of 65,000 women and found that women who
ate the most easily digestible and readily absorbed
carbohydrates (highest glycemic index)were 47
percent more likely to acquire type 2 diabetes than
those with the lowest average glycemic-index score.