BIOCHEMISTRY | LECTURE - CARBOHYDRATES AND GLYCOBIOLOGY

MIDTERMS

1ST SEMESTER - AY 2022-2023

BSMLS-2A

SUGARS: STRUCTURE & STEREOCHEMISTRY ➔ Note: as long as the monosaccharides have 3

CARBOHYDRATES carbons they will be called as triose even if they have
ketones/aldehydes as their main functional groups
➔ In scientific literature, sugar is also known as ➔ Triose w/ aldehyde (aldotriose); triose w/ ketones
carbohydrate (or hydrate of carbon) and saccharides (ketotriose)
➔ Most abundant biomolecules on Earth ◆ Glyceraldehyde (simplest aldotriose) –
◆ Each year, photosynthesis converts >100 multiple hydroxides (poly)
billion tons of CO2 and H2O into ◆ Dihydroxyacetone (simplest ketotriose)
carbohydrates
◆ Certain carbohydrates are a dietary staple of
most parts of the world i.e., Filipino = rice
covered with starch (carbohydrate)
➔ Oxidation of carbohydrates – a central energy yielding
pathway in most non-photosynthetic cells
➔ Insoluble carbohydrate polymers serve as structural
and protective elements in the cell walls of bacteria,
plants and in the CT of animals
◆ Lubricates skeletal joints and participates in
recognition and adhesion between cells
➔ most complex carbohydrate polymers are covalently
attached to proteins/lipids that act as signals
➔ Has three major size classes:
◆ monosaccharides
◆ oligosaccharides
◆ polysaccharides FUNCTIONAL GROUP NAME
➔ Polyhydroxyaldehydes (aldose) or
polyhydroxyketones (ketose) Aldehyde (-COH) Aldose
➔ Name ends in -ose (i.e., sucrose, fructose, ribose,
aldose) Ketone (CH-CO-CH) Ketose
➔ Many, but not all, have the empirical formula: (CH2O)n
◆ Some contain nitrogen, phosphorous, or
sulfur Number of Carbon Aldose Ketose
◆ The water / H2O is known as “hydrate”
3 aldotriose ketotriose
(hydrates the carbon) = carbo-hydrate
➔ Play a number of important roles in biochemical 4 aldotetrose ketotetrose
processes
◆ Major sources of energy (go foods in go, 5 aldopentose ketopentose
grow, & glow)
◆ Have a key role in cell surfaces such as 6 aldohexose ketohexose
cell-cell interactions and immune recognition
◆ Essential structural components 7 aldoheptose ketoheptose

MONOSACCHARIDES ➔ Monosaccharides also exhibit stereoisomerism

WHAT IS UNIQUE ABOUT THE STRUCTURE OF SUGARS? ◆ Stereoisomerism – the difference in the
configuration of a chemical structure in
➔ Monosaccharides: monomers (building blocks) of all space; differ from each other in configuration
carbohydrates; one unit of saccharide ◆ Simplest carbohydrate that exhibits
➔ Called differently depending on the number of stereoisomerism (superimposable) is
carbons and main functional group. glyceraldehyde
➔ Simplest monosaccharides contain three carbons ➔ Mirror-image stereoisomers (rotates differently/chirals)
(triose) disregarding the functional group attached are called enantiomers.
 ◆ (e.g., D&L glucose)
➔ Non mirror-image stereoisomers (achirals but can NUMBERING OF CARBON ATOMS IN SUGARS
also be a chiral) are called diastereomers
➔ Configuration: three-dimensional arrangement of
groups around the chiral carbon.
◆ Chiral carbon - is a carbon that contains four
different groups attached to it.

➔ Stereoisomers differ from each other in configuration.

◆ D & L system is widely used
◆ R,S system is also used, a more recent
system
● No one-to-one correspondence
between the two systems (e.g.,
some D-isomers are R, while others
are S)
➔ Stereoisomerism of carbohydrates
(monosaccharides): Possibilities for stereoisomerism
increase as the number of carbon atoms increases
(>3)
➔ To show structures of the molecules, Fischer
projection is used.
◆ Fischer projection – developed by Emil
Fischer during 1980s / 1970s
◆ Shows the two-dimensional perspective of
the molecular structure; best projection for
linear carbohydrates (able to distinguish
glucose, galactose, etc. or if its L or D
molecule)
➔ In a Fischer projection, the orientation of the bonds
represent the direction of the bond
◆ Vertical bonds: directed behind the plane
(away from the viewer)
◆ Horizontal bonds: directed in front of the
plane (towards the viewer)
(a) Examples of an aldose (D-glucose) and a ketose (D-fructose), showing the
numbering of carbon atoms. (b) A comparison of the structures of D-glucose and
L-glucose.
➔ Most highly oxidized carbon is in located/written on
the top that is involved in the aldehyde group (due to
double bond), designated as the carbon 1
➔ While on the ketose, the ketone group is designated
as carbon 2
➔ Note: in determining whether a particular
monosaccharide is a D/L always look at the second to
the last carbon (penultimate carbon)
➔ The designation of the D/L depends on the
arrangement of the chiral carbon w/ the highest
oxidized carbon number; should always be the
penultimate carbon or the second to the last carbon
➔ D if the OH is on the right side of the penultimate
carbon
➔ L if the OH is on the left side of the penultimate
carbon

➔ Wedge bond – directed towards the back (vertical)

➔ Solid bond – directed towards the viewer (horizontal)

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STEREOISOMERS OF AN ALDOTETROSE
Sugars: all of the carbon in the middle has hydroxyl group
(polyol structure)
Possible stereoisomers for and aldotetrose:
➔ Aldotetrose have two chiral
atoms/carbons
➔ 22 for aldotetrose or 4 possibilities
of a stereoisomer (possible to
create mirror images of the 2
d-isomers)
◆ D-erythrose → L-erythrose
◆ D-threose → L-threose
➔ The two D configurations (d-erythrose & d-threose)
has the same configuration at carbon 3 but they have
different configurations (arrangements)
◆ (carbon 3) both the -OH are situated on the
right side while the -OH at the carbon 2 are
located on different sides, thus when you
superimpose these two they will not be a
mirror-images at each other (diastereomers)
◆ Therefore:
● D & L -Erythrose / D & L -Threose =
enantiomers
● D-Erythrose & D-Threose = are cyclic not linear
diastereomers of each other
➔ Diastereomers that differ from each other in the
configuration (only one chiral carbon) are called
“epimers”
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Aldoses containing from three to six carbon atoms, with the
numbering of the carbon atom shown. Note that the figure
shows only half the possible isomers. For each isomer shown,
there is an enantiomer that is not shown, the L-series.
➔ Most of the carbohydrates that exist in the body are
aldohexoses (i.e., D-glucose)
◆ Glucose is a ubiquitous energy source
◆ Ribose (D-Ribose) plays an important role in
the structure of nucleic acids
➔ Ketotriose are not that abundant (in the body) except
for sugar (sucrose) where it’s a dimer of glucose and
fructose (ketohexose)
WHAT HAPPENS IF A SUGAR FORMS A CYCLIC
MOLECULE?
➔ Sugars (especially 5-6 C) normally exist as cyclic
molecules when they are found in the body.
◆ All, if not most, carbohydrates in the body
➔ Cyclization is a result of interaction between
functional groups
◆ C1 (aldehyde) and C5 (alcohol) forms cyclic
hemiacetal (aldohexoses)
◆ C2 (ketone) and C5 (alcohol) forms cyclic
hemiketal (ketohexoses)
➔ Once a cyclic structure is formed between the
reaction of the aldehyde and an alcohol, the carbonyl
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 carbon becomes a new chiral center: anomeric
carbon
➔ Cyclic sugar can take two different forms (α and β)
and are called anomers of each other.
➔ The close proximity of C5 to C1 will allow the
cyclization process of a hemiacetal formation to
undergo
➔ The formation of hemiacetals is relatively unstable
HAWORTH PROJECTION FORMULAS
➔ α – if the OH is projected downwards
◆ α-D-Glucopyranose
➔ β – if the OH is projected upwards
◆ β-D-Glucopyranose
FISCHER PROJECTION FORMULAS OF THE THREE
FORMS OF GLUCOSE
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➔ α – if the OH is on the right
◆ α-D-Glucose
➔ β – if the OH is on the left
◆ β-D-Glucose
➔ D and L is usually established before the cyclization
NOTE that the α and β forms can be converted to each
other through the open-chain form. The configuration at
carbon 5 determines the D designation.
➔ Fischer projection formulas are useful for
describing stereochemistry of sugars in their linear
forms (open chain form)
➔ Haworth projection formulas are more useful in
describing cyclic structure.
◆ Structures are viewed from the edge of the
plane.
◆ Five-membered rings are called furanose
◆ Six-membered rings are called pyranose
HAWORTH REPRESENTATIONS OF SUGAR STRUCTURES
(a) A comparison of the structure of furan with Haworth representations
of furanoses. (b) A comparison of the structure of pyran with Haworth
representations of pyranoses. (c) α-D-Glucopyranose in the Haworth
representation (left), in the chair conformation (middle), and as a
space-filling model (right).
A COMPARISON of the Fischer, complete Haworth, and
abbreviated Haworth representations of f α- and
β-D-glucose (glucopyranose) and β-D-ribose
(ribofuranose).
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 ➔ TWO TYPES OF REAGENTS are used to detect the
presence of reducing sugars: silver ammonia complex
ion, Ag(NH3)2+ (Tollen’s test) and glucose oxidase
(which is specific only for glucose).

Oxidation of a sugar to a lactone. An example of an

oxidation reaction of sugars: oxidation of α-D-glucose
hemiacetal to give a lactone. Deposition of free silver as a
silver mirror indicates that the reaction has taken place.
➔ H is removed from OH in C1; hemiacetal becomes a
ketone? (lactone)

A silver mirror produced by an aldehyde. After the addition

of Tollens reagent to an aldehyde, a silver mirror has been
deposited in the inside of this test tube.
➔ Ag2+ ions from Ag(NH 3)2+ will be seen floating to the
top

In the Fischer representation, the α-anomer is represented

with the OH group (red) to the right, and the β-anomer is
represented with the OH group(red) to the left.

In the Haworth representation, the α-anomer is represented

with the OH group (red) downward, and the β-anomer is
represented with the OH group(red) upward.

➔ α and β – anomers
➔ L and D – stereoisomers

REACTIONS OF MONOSACCHARIDES
What are some oxidation-reduction reactions of sugars?
➔ Redox reaction of sugars play key roles in
biochemistry
◆ Oxidation: releases the energy stored in
carbohydrates, takes place in cellular
respiration
◆ Reduction: forms the carbohydrate, takes ➔ There are also reduced sugars (oxidizing sugars) that
place in photosynthesis (plants, bacteria, are biochemically important
algae) ◆ A deoxy sugar, L-fucose, is found in the
➔ Oxidation reaction of sugars are used to identify the carbohydrate portions of glycoproteins
sugar including the ABO blood-group antigens
◆ Aldehydes can be oxidized to give carboxyl ● A deoxy sugar does not contain an
group of acids (-COO-), used to test for oxygen; a hydrogen atom is
aldoses substituted by for one of the
◆ Aldoses are called reducing sugars hydroxyl groups of the sugar
◆ In the cyclic form, the compound formed by
the oxidation of aldose is called a lactone.

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 ● L-fucose or
6-Deoxy-L-beta-Galactose
◆ Another deoxy sugar, β-D-Deoxyribose or
2-Deoxy-β-D-ribose, is found in DNA
Structures of Two Deoxy Sugars
The structures of the parent sugars are shown for comparison.
➔ When the carbonyl group of a sugar is reduced to
a hydroxyl group, the resulting polyol is known as an
alditol.
C=O → C-OH
➔ Hydrogenation (addition of hydrogen) is a
form of reduction
➔ Two well-known alditols are economically important:
xylitol and sorbitol (e.g., artificial sweeteners)
VITAMIN C IS RELATED TO SUGARS
➔ Also known as ascorbic acid
➔ Vitamin C is an unsaturated lactone with a five
membered ring structure.
➔ Most animals synthesize Vitamin C except for
guinea pigs and primates, including humans.
➔ Ascorbic acid is taken through diet; deficiency leads
to scurvy (characterized by dysfunctional/weakened
collagen)
1. SCURVY: collagen (protein) has structural defects,
causing skin lesions and fragile blood vessels.
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Hydroxyproline (amino acid derivative) is important for
the stability of collagen.
2. Ascorbic acid is essential for the activity of prolyl
hydroxylase, which converts proline to hydroxyproline.
3. Lack of ascorbic acid affects this activity, leading to
the fragile collagen responsible for the symptoms of
scurvy
1600s/1700s: sailors would put citrus in their cargo to
prevent scurvy
WHAT ARE SOME IMPORTANT ESTERIFICATION
REACTIONS OF SUGARS?
➔ Hydroxyl groups of sugars can react with acids and
derivatives of acids to form esters.
➔ Phosphate esters are important because they are
the usual intermediates in the breakdown of
carbohydrates to provide energy.
◆ Formed by the transfer of phosphate from
ATP to give phosphorylated sugar and ADP.
➔ These reactions are important in carbohydrate
metabolism.
The Formation of a Phosphate Ester of Glucose
ATP is the phosphate group donor. The enzyme specifies the
interaction with –CH2OH on carbon 6.
WHAT ARE GLYCOSIDES AND HOW DO THEY FORM?
➔ It is possible for a sugar hydroxyl group (ROH)
bonded to the anomeric carbon to react with another
hydroxyl group (R’-OH) to form a glycosidic linkage
(R’-O-R), or a compound known as a glycoside.
◆ Glycosidic linkage is not an ether
◆ The hydrolysis of glycosidic linkages results
in the original alcohol, not a new compound.
➔ The bond formed is called a glycosidic bond.
An Example of the Formation of a Glycoside
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 Methyl alcohol (CH3OH) and an α-Dglucopyranose react to
form the corresponding glycoside.
➔ CH3 will form on the hemiacetal producing a full acetal
+ H2O (previously methyl alcohol)
➔ If water is reintroduced to the structure, the
resulting structure will be the original alcohol
(magbalik lang siya sa original structure prior to the
reaction)
—
➔ Glycosidic bonds formed through the linkage of the O
atom of one sugar to another are called O-glycosidic
bonds
◆ N-glycosidic bonds can be found in nucleic
acids, especially between the nitrogenous
bases and the five-carbon sugar
◆ S-glycosidic bonds are found in
thioglycosides, where O is replaced by sulfur
➔ Glycosides derived from furanose (5 C): furanosides
➔ Glycosides derived from pyranose (6 C):
pyranosides
➔ Glycosidic bonds between monosaccharides are
the basis for the formation of oligosaccharides
and polysaccharides
➔ Glycosidic linkage can take various forms; numerous
combinations are found in nature.
➔ The hydroxyl groups (-OH) are numbered so that they
can be distinguished; the numbering follows the
carbon atoms.
Two Different Disaccharides of α-D-glucose.
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These two chemical compounds have different properties
because one has an α(1→4) linkage and the other has an
α(1→6) linkage.
➔ α(1→4): -OH projects downwards
◆ The glycosidic linkage occurs between C1 of
the first anomer and C2 of the second
anomer
➔ α(1→6): the curvature of alpha (distinguishing feature)
indicates that the anomer is alpha; if straight lang,
then beta
➔ These linkages determine the nature, reactivity, and
the structure of polysaccharides and oligosaccharides
➔ All of the properties of polysaccharides rely on the
existing glycosidic bond between monomeric units
A Disaccharide of β-D-glucose
➔ The curvature from the first anomer is originally going
upwards (beta) pero naging downward lang ang curve
to connect to the second anomer
➔ Usually, in the formation of a glycosidic bond, there
are repeating monomeric units
◆ If alpha magstart, then it will always be
alpha-alpha-alpha (same goes with beta)
Both anomeric carbons (C-1) are involved in the glycosidic
linkage.
➔ Chemical nature of oligosaccharides and
polysaccharides depend on
1. the monosaccharides that are linked
together
2. the particular glycosidic bond formed
➔ EXAMPLE: the difference between cellulose and
starch depends on the glycosidic bond formed
between glucose monomers.
◆ Variation in glycosidic linkages can form
linear and branched chain polymers
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The linear polyglucose chain occurs in amylose. All glycosidic
bonds are (1 → 4).

A disaccharide with a free hemiacetal end is a reducing sugar

because of the presence of a free anomeric aldehyde carbonyl
or potential aldehyde group.

WHAT ARE SOME OTHER IMPORTANT DERIVATIVES OF

SUGARS?

The branched-chain polymer occurs in amylopectin and ➔ AMINO SUGARS: carbohydrates that contain amino
glycogen. Branched polyglucose-chain glycosidic bonds are (1 group or its derivatives that substitutes for the
→ 6) at branched points, but all glycosidic bonds along the hydroxyl group of the parent sugar
chain are (1 → 4). ◆ In N-acetyl amino sugars, the amino group
itself carries the acetyl group (CH3-CO-) as a
➔ In testing the presence of reducing sugars, the substituent
anomeric carbon is usually involved in the reaction. It ➔ Important examples of amino sugars:
is also frequently involved in the glycosidic linkage. N-acetyl-β-D-glucosamine and N-acetyl-βmuramic
➔ Note that the internal anomeric carbon in an acid. These are components of bacterial cell walls.
oligosaccharide or a polysaccharide is not free to give
a positive result for reducing sugar. The structures of N-acetyl-β-D-glucosamine and
➔ Only if the end residue is a free hemiacetal rather N-acetylmuramic acid.
than a glycoside will there be a positive test for
reducing sugar.
◆ Even though a particular polysaccharide in
oligosaccharide contains a reducing sugar
such as glucose, if the anomeric carbon
where the aldehyde is supposedly found is
not available (it’s participating in the
formation of a glycosidic chain), then it would
not yield a positive result for reducing sugars
◆ Nonreducing end = negative
◆ Reducing end (free hemiacetal/anomeric
aldehyde carbonyl) = positive

Reducing Sugars Some hexose derivatives that are important in biology.

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➔ In amino sugars, an -NH2 group replaces one of the
-OH groups in the parent hexose.
➔ Substitution of -H for -OH produces a deoxy sugar;
note that the deoxy sugars shown here occur in
nature as the L-isomers.
➔ The acidic sugars contain a carboxylate group, which
confers a negative charge at neutral pH.
➔ D-glucono-δ-lactone results from formation of an ester
linkage between the C-1 carboxylate group and the
C-5 (also known as the carbon) hydroxyl group of
D-gluconate.
OLIGOSACCHARIDES
SOME IMPORTANT OLIGOSACCHARIDES
➔ Oligomers (Grk. oligos = few) of sugars are usually
disaccharides formed by linking two
monosaccharides units.
◆ 2 or 3-9 monosaccharide units
➔ Three of the most important examples of
oligosaccharides are disaccharides
◆ Sucrose
● Made up of glucose and fructose
connected at an α (1–2) glycosidic
linkage
◆ Lactose
● Disaccharide composed of a
galactose and glucose where
galactose is connected to glucose
in the β (1–4) glycosidic linkage
◆ Maltose
● Composed of 2 α-D-glucose
connected at an α (1–4) glycosidic
bond
The Structure of Several Important Disaccharides
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➔ Cellubiose is composed of 2 glucose connected at β
(1–4) glycosidic linkage
➔ Isomaltose is composed of 2 glucose connected at α
(1–6) glycosidic linkage
➔ Note that the notation —HOH means that the
configuration can be either α or β.
➔ When a D sugar is drawn in this orientation, if the
—OH group is above the ring, the configuration is
termed β.
➔ The configuration is termed α if the —OH group is
below the ring.
➔ Also note that sucrose has no free anomeric carbon
atoms.
WHAT MAKES SUCROSE AN IMPORTANT COMPOUND?
➔ Sucrose (table sugar) is extracted from sugar cane
and sugar beets.
➔ Monosaccharide units: α-D-glucose & β-D-fructose.
➔ C-1 of the glucose is linked to the C-2 of the fructose
in a α, β(1 → 2) glycosidic linkage.
◆ alpha in the first carbon
◆ beta in the second orientation of the
anomeric carbon
➔ Not a reducing sugar, but monomeric substituents
(glucose and fructose) are.
➔ Consumption leads to hydrolysis of monomers which
are then used as energy sources.
◆ Glucose is directly involved in glycolysis
◆ Fructose is isomerized to glucose; energy
input before fructose is utilized by the body
➔ Humans consume large quantities; excessive
consumption contribute to health problems which led
to a search for other sweetening agents
◆ Fructose: sweeter than sucrose, but changes
texture of food
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 ◆ Saccharin and cyclamates: causes cancer in ◆ Cellobiose (can't be digested) = beta linkage
lab animals ➔ Yeast contains enzymes that hydrolyze starch to
◆ Aspartame: suspected to cause neurological maltose then glucose, which is fermented during
problems brewing.

THE CASE OF LACTOSE INTOLERANCE

➔ Sugar intolerance results from the inability to either

digest or metabolize certain sugars, usually due to
missing or defective enzymes.
OTHER IMPORTANT DISACCHARIDES TO HUMANS ➔ Some adults have a deficiency in the enzyme lactase
in the intestinal villi.
LACTOSE ◆ Lactase hydrolyzes lactose into galactose
and glucose in the intestinal villi of the
digestive system
➔ Absence of lactase → Build-up of lactose causes
bacterial lactase to act on it, releasing H, CO2, and
organic acids instead of galactose and glucose.
➔ The bacterial products lead to digestive problems
such as bloating and diarrhea; the products further
draw water via osmosis thus aggravating the diarrhea.

➔ Made up of β-D-galactose and D-glucose linked at

β(1→4)
➔ A reducing sugar because the anomeric carbon of
glucose is free.
◆ Free to yield a carboxyl group for a positive
result
➔ Have two anomeric forms, each must have the
β-D-galactose while the D-glucose can be either α or
β.

MALTOSE
➔ Even if lactase is present, other people cannot
metabolize galactose.
➔ If an enzyme that catalyzes the reaction pathway for
galactose is absent, galactose builds up resulting in
galactosemia.
◆ Severe problem in infants because galactose
is converted to galactitol, which cannot be
excreted. The accumulation draws in water
and causes swelling, edema causes damage
to the tissue

➔ Maltose is obtained from the hydrolysis of starch

➔ Consist of two residues of D-glucose in an α(1→4)
linkage.
➔ Differs from cellobiose (from cellulose) only in the
glycosidic linkage which is β(1→4)
➔ Mammals can digest maltose but not cellobiose.
◆ Maltose (can be digested) = alpha linkage

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 ➔ Animals are not capable of hydrolyzing cellulose
because of the absence of cellulase.
◆ Cellulase attack the β(1→4) glycosidic bonds
◆ Certain bacteria have cellulase, including
bacteria found in termite gut and ruminants
(animals that have 4 chambers in their
stomach; i.e., cows, goats).
● Termites have cellulase → can eat
wood → degrades cellulose into
cellobiose → glucose
➔ Dietary therapy for lactose intolerance and ◆ Cellobiose is the disaccharide that is yielded
galactosemia are different. from the metabolism of cellulose
◆ Lactose intolerant people must avoid taking
in lactose throughout their lives. The Polymeric Structure of Cellulose
◆ Galactosemia-afflicted people must avoid
milk during their childhood. The development
of metabolic pathways for galactose during
puberty alleviates the problem in most
individuals.
● In most cases, mawala lang once
magmature na ang metabolic
pathways for galactose (During
puberty and onwards)

POLYSACCHARIDES
STRUCTURES AND FUNCTIONS OF POLYSACCHARIDES

➔ When many monosaccharides are linked together, the

result is a polysaccharide.
➔ Polysaccharides that occur in organisms are usually
composed of a very few types of monosaccharide.
◆ Homopolysaccharide: polymer consisting
of only one type of monosaccharide.
◆ Heteropolysaccharide: polymer consisting
of more than one type of monosaccharide.
➔ Complete characterization of a polysaccharide
includes
◆ Specification of which monomers are present
◆ Sequence of monomers
◆ Specific type of glycosidic linkage
HOW DO CELLULOSE AND STARCH DIFFER FROM ONE
ANOTHER?
2 Important Polysaccharides: Cellulose and Starch
β-Cellobiose is the repeating disaccharide. The monomer of
cellulose is the β-anomer of glucose, which gives rise to long
chains that can hydrogen-bond to one another.
STARCH
➔ Starch are polymers of α-D-glucose. Has different
forms; can be distinguished from one another by their
degrees of chain branching.
◆ Amylose: linear polymer linked at α(1→4)
glycosidic bonds
◆ Amylopectin: branched chain polymer with
branches starting at α(1→6) linkages along
the chain of α(1→4)

CELLULOSE
➔ Cellulose is the major structural component of plant
cell walls.
◆ Linear homopolysaccharide of β-D-glucose,
with all residues linked in β(1→4) glycosidic
bonds.
◆ Individual polysaccharide chains are
hydrogen-bonded together.

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 Amylose and Amylopectin are the Two Forms of Starch

Note that the linear linkages are α(1→4), but the branches in
amylopectin are α(1→6).
➔ Branches in polysaccharides can involve any of the
hydroxyl groups on the monosaccharide components.
➔ Amylopectin is a highly branched structure, with
branches occurring at every 12 to 30 residues.

The monomer of starch is the αanomer of glucose, which gives

rise to a chain that folds into a helical form. The repeating
dimer has α(1→4) linkages throughout.
➔ Iodine settles on the hole inside the helix
➔ Starch are storage molecules and therefore should
have a mechanism for releasing glucose.
◆ Enzymes can hydrolyze these different forms
of starch: α and β-amylase. The Starch-Iodine Complex.
◆ β-amylase is an exoglycosidase, cleaves Amylose occurs as a helix with
from the non-reducing end of the polymer, six residues per turn. In the
produces maltose. starch–iodine complex, the iodine
● Starts sa beginning ng chain molecules are parallel to the long
(non-reducing end) axis of the helix. Four turns of the
◆ α-amylase is an endoglycosidase, cleaves helix are shown here. Six turns of
anywhere along the chain to produce the helix, containing 36 glycosyl
glucose and maltose. residues, are required to produce
➔ Amylose can be completely degraded to glucose the characteristic blue color of
and maltose by the two amylases; amylopectin is the complex.
not completely degraded because the branches are
not attacked.
◆ The branches that contain the (1→6)
glycosidic bonds cannot be hydrolyzed by
the α- and β-amylase
◆ Debranching enzymes that attack α(1→6)
are used by plants and animals.
● Removal of the α(1→6) glycosidic
linkage

The Structure of Starch is Based on the α-anomer of

Glucose

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BARBA, DAYRIT, PATERNO, SOLIJON | 12
HOW IS GLYCOGEN RELATED TO STARCH? solution is, the faster energy can be
released.
2. When an organism needs energy quickly for
spontaneous reflexes, the enzyme glycogen
phosphorylase has more potential targets if
there are more branches. This allows quicker
mobilization of glucose
a. Glycogen phosphorylase cleaves
off glycogen from its structure to
yield glucose

WHAT IS CHITIN?
➔ Starch is to plants as glycogen is to animals: both are
storage polymers.
➔ Glycogen is a branched-chain polymer of
α-D-glucose; similar to the amylopectin part in this
regard.
◆ Glycogen is more highly branched, every
10th residue is a branch compared to every
25th in amylopectin
◆ Average chain length is 13 glucose
residue, and 12 layers of branching
◆ Has glycogenin at its core, an enzyme that
acts as a primer to convert glucose into
glycogen.
➔ Found in animal cells in granules, observed in liver
and muscle cells. CHITIN
➔ polysaccharide similar to cellulose in both structure
A Comparison of the Degrees of Branching in Amylopectin and function.
and Glycogen ◆ Linear homopolysaccharide with all residues
linked in β(1→4) glycosidic bonds
➔ Differ from cellulose in the monomeric unit.
◆ cellulose: β-D-glucose
◆ chitin: N-acetyl-β-D-glucosamine
➔ Plays a structural role, has a fair amount of
mechanical strength because of hydrogen bonds.
◆ Major component of the exoskeletons of
invertebrates; cell walls of algae, fungi, and
yeast.

A core protein of glycogenin is

surrounded by branches of glucose
units. The entire globular complex
may contain approximately 30 000 The Polymeric Structure of Chitin
glucose units.

➔ The number of branch

points in the glycogen structure is
significant for two reasons:
1. A more branched polysaccharide is more
water-soluble; the more glycogen in a

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BARBA, DAYRIT, PATERNO, SOLIJON | 13
N-Acetylglucosamine is the monomer, and a dimer of
N-acetylglucosamine is the repeating disaccharide.

WHAT ROLE DO POLYSACCHARIDES PLAY IN THE

STRUCTURE OF CELL WALLS?

HETEROPOLYSACCHARIDES
➔ Heteropolysaccharides are major components of
bacterial cell walls.
◆ They are also cross-linked by peptides in
prokaryotic cell walls.
◆ The repeating polysaccharide units consist
of two residues held at β(1→4) like cellulose.
◆ Residues are N-acetyl-D-glucosamine and
N-acetylmuramic acid.
➔ N-Acetylmuramic acid is found only in prokaryotic cell
walls; does not occur in eukaryotic cell walls.
➢ Plants: cellulose; bacteria: heteropolysaccharides

The Structure of Peptidoglycan of the Bacterial Cell Wall of

Staphylococcus aureus

(a) The repeating disaccharide. (b) The repeating disaccharide

with the tetrapeptide side chain (shown in red). (c) Adding the
pentaglycine cross-links (shown in red). (d) Schematic diagram
of the peptidoglycan. The sugars are the larger spheres. The

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BARBA, DAYRIT, PATERNO, SOLIJON | 14
red spheres are the amino acid residues of the tetrapeptide,
and the blue spheres are the glycine residues of the
pentapeptide.

Glycosaminoglycans, which are formed from repeating

disaccharide units, often occur as components of the
proteoglycans

Structures and Roles of Some Polysaccharides

➔ Plant cell walls consist largely of cellulose.
➔ PECTIN, another component of plant cell walls, is Polymer Type Repeatin Size (# of Roles/sig
composed mostly of D-galacturonic acid residues. g Unit monosac nificance
charide
◆ Extracted from plants; used as a gelling
units)
agent in yogurt fruit preserves, jams, and
jellies Starch (α1→4)Gl
◆ C6 contains carboxylic acid (-COOH) instead Amylose Homo- c, linear
of alcohol Amylopec Homo- (α1→4)Gl
➔ LIGNIN (L. lignum, “wood”), a nonpolysaccharide tin c, with
component of plant cells walls; a polymer of coniferyl (α1→6)
alcohol, very tough and durable Glc
branches
◆ Gives resistance to wood
every
24-30
DO POLYSACCHARIDES PLAY ANY SPECIFIC ROLES IN residues
CONNECTIVE TISSUE?
Glycogen Homo- (α1→4)Gl
GLYCOSAMINOGLYCANS c, with
➔ Polysaccharide based on a disaccharide in which one (α1→6)
Glc
of the sugars is
branches
◆ An amino sugar every
◆ One of the sugars has a negative charge 8-12
because of a sulfate or a carboxyl group residues
➔ Derivatives of a monosaccharide
➔ Involved in a wide variety of cellular function and Cellulose Homo- (β1→4)Gl
tissue. c
◆ Heparin: a natural anticoagulant that
Chitin Homo- (β1→4)Gl
prevents blood clots
cNAc
◆ Hyaluronic acid: a component of vitreous
humor of the eye and the lubricating fluid of Dextran Homo-
the joints
◆ Chondroitin sulfates and keratan sulfate: Peptidogly Hetero-;
component of connective tissues can peptides
◆ Glucosamine sulfate and chondroitin attached
sulfate: OTC drugs that help repair
damaged cartilage Agarose Hetero-

Hyaluronat Hetero-;
e acidic

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BARBA, DAYRIT, PATERNO, SOLIJON | 15
 ◆ LOC inside of the cell: Golgi complexes,
secretory granules, lysosomes
➔ Highly rich in information; forms specific sites for
recognition and high-affinity binding by other proteins.

GLYCOCONJUGATES:,PROTEOGLYCANS,
GLYCOPROTEINS, & GLYCOLIPIDS
GLYCOCONJUGATES
PROTEOGLYCANS
➔ Carbohydrates attached to other biomolecules ➔ Bigger and heavier in terms of mass
➔ Aside from being energy storage and structural ➔ Macromolecules of the cell surface of extracellular
materials, sugars are also information carriers: matrix, a type of glycoprotein
◆ They serve as destination labels for some ◆ Unique from other glycoproteins because of
proteins glycosaminoglycan.
◆ They serve as mediator of specific cell-cell ● Has glycosaminoglycan instead of
interaction and interaction between cells and disaccharide
extracellular matrix ◆ One or more glycosaminoglycan chains are
➔ Other roles of specific carbohydrate-containing joined covalently to a membrane protein
molecules include ◆ Glycosaminoglycan moiety of the
◆ cell-cell recognition proteoglycan dominates the structure; often
◆ cell adhesion the main site of biological activity
◆ cell migration ◆ Major components of connective tissues
◆ blood clotting such as cartilage
◆ immune response ● Drugs that repair CT mostly have
➔ When an informational carbohydrate is covalently GAGs as their component
bonded to a protein or lipid, it forms a
glycoconjugate. The Transmembrane Proteoglycans

WHAT ARE THE DIFFERENT GLYCOCONJUGATES?

GLYCOPROTEINS
➔ Proteins that contain carbohydrates in anywhere
through their structure
➔ Have one or several oligosaccharides covalently
joined to a protein (which serves as an anchor/core of
the structure).
◆ The oligosaccharides have various
complexity depending on the molecule.
◆ LOC outside of the cell: on the outer face of
the plasma membrane, in the extracellular
➔ The four syndecans in the center are full-time
matrix, and blood
proteoglycans that are usually substituted with

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BARBA, DAYRIT, PATERNO, SOLIJON | 16
 heparan sulfate chains (dark blue) toward their N
termini. Syndecans-1 and -3 sometimes possess
additional chondroitin sulfate chains ( pink).
➔ The melanoma chondroitin sulfate proteoglycan/NG2
( green) has one chondroitin sulfate chain and is also
a full-time proteoglycan.
➔ The remainder are part-time proteoglycans. The
alternately spliced extracellular segment of CD44 may
bear one heparan sulfate chain.
➔ Neuropilin-1 and betaglycan can be substituted with
either heparan or chondroitin/ dermatan sulfate
(purple)
GLYCOLIPIDS
➔ Membrane lipids in which the hydrophilic head groups
are oligosaccharides
◆ Act as a specific site for recognition by
carbohydrate-binding proteins.
◆ Gangliosides are a specific type of
glycolipid and the carbohydrate moieties are
available for signal transduction.
ABO BLOOD GROUPS
➔ The antigenicity/antigenic determinant nature of
carbohydrates is involved in the blood groups
➔ The four blood groups are distinguished based on the
oligosaccharide portion of the glycoprotein on the
surface of red blood cells.
◆ In all blood types, L-fucose
(6-deoxy-L-galactose) is found
◆ N-Acetylgalactosamine is found at the
nonreducing end of the oligosaccharide in
the type-A blood-group antigen
◆ In type-B blood, α-D-galactose takes the
place of N-acetylgalactosamine
◆ In type-O blood, neither of these terminal
residues is present
◆ In type-AB blood, both kinds of
oligosaccharide are present
➔ If a blood transfusion is attempted with incompatible
blood type, an antigen-antibody reaction takes
place
◆ The antibodies on the recipient recognize the
antigen specific for the introduced blood from
the donor.
◆ The characteristic oligosaccharide residues
on the introduced blood serve as the antigen
➔ A cross-linking reaction occurs; cells will clump
together
➔ Wrong blood transfusion can result to life-threatening
severe reaction

Carbohydrates present in the plasma membrane as short,

sometimes branched, chains of sugars attached either to
exterior peripheral proteins (forming glycoproteins) or to the
polar ends of phospholipid molecules in the outer lipid layer
(forming glycolipids).

CARBOHYDRATES AND THE IMMUNE RESPONSE

➔ Some of the most important examples of

glycoproteins are involved in the immune response
(e.g., antibodies)
◆ Antibodies bind to immobilize antigens that
attack the organism.
◆ Carbohydrates serve as the antigen—the
communicating factor
➔ Carbohydrates also play an important role as
antigenic determinants:
◆ portions of an foreign molecule that
TRANSFUSION RELATIONSHIPS
antibodies recognize and to which they bind.
Blood Type Makes Can Receive Can Donate
Antibodies From To

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BARBA, DAYRIT, PATERNO, SOLIJON | 17
 Against

O A, B O O, A, B, AB

A B O, A A, AB

B A O, B B, AB

AB None O, A, B, AB AB

O – universal donor
AB – universal receiver

OPRAHHHHHHHHH putangina

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