Module on Carbohydrates

CHEM41 and 43 Lecture Course Guide

Department of Physical Sciences and Mathematics

College of Arts and Sciences, University of the Philippines Manila

Carbohydrates
Introduction
Carbohydrates are the most abundant class of bioorganic molecules on earth. Along with
proteins and  fats, carbohydrates are one of three main nutrients found in many foods. Many
commonly encountered carbohydrates are polysaccharides, like glycogen, starch and cellulose.
Our body breaks down starch and glycogen into glucose which can be used immediately as
source of energy or stored in the liver and muscles for later use. Moreover, carbohydrates are
metabolic precursors of virtually all other molecules, e.g. amino acids, fats, etc.

Learning Objectives
The student should be able to:

1. Relate the structures, properties, and reactivities to the functions of carbohydrates;

2. Perform isolation of glycogen from chicken liver;

3. Interpret results of carbohydrate qualitative tests; and

4. Estimate glucose content of commercially available drinks.

*Objectives 2-4 are Laboratory Objectives

Reference Textbooks:
1. Nelson, D., Cox, M. (2008). Lehninger Principles of Biochemistry, 5th Ed. New York:
W.H. Freeman and Company.

2. Berg, J., Tymoczko, J., Stryer, L., Gatto, G. (2012). Biochemistry, 7th Ed. New York:
W.H. Freeman and Company.

3. Voet, D. & Voet, J. (2011). Biochemistry. (4th ed). United States of America: John
Wiley & Sons, Inc.

4. Campbell, M.K. & Farrell, S.O. (2012). Biochemistry. (7th ed). Belmont, CA, USA:
Brooks/Cole Cengage Learning.

Supplemental Readings:
1. Carbohydrates - Structure and Function ([Link]
shainamavreenvillaroza/chem-45-biochemistry-carbohydrates)

2. Carbohydrates - Chemical Properties (slides 48-64) ([Link]

ashokktt/carbohydrate-chemistry-37049261)

I. Functions of Carbohydrates
• An energy storage; plants convert light energy into monosaccharides and starch which
animals can use as energy source.

• Structure of organisms: cellulose, chitin and bacterial cell wall

• Component of nucleic acid: ribose, deoxyribose

• Carbohydrate “markers” on cell surfaces play key roles in cell-cell recognition

processes

• Carbohydrates linked to lipid molecules (glycolipids) are common components of

biological membranes

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Module on Carbohydrates
CHEM41 and 43 Lecture Course Guide
Department of Physical Sciences and Mathematics

College of Arts and Sciences, University of the Philippines Manila

• Carbohydrates covalently linked to proteins (glycoproteins) are important components

of cell walls and extracellular structures in plants, animals and bacteria

• Carbohydrates are the metabolic precursors of virtually all other molecules

II. Structure, Nomenclature and Classification

By definition, carbohydrates are polyhydroxy aldehydes and polyhydroxy ketones or
compounds that produce such substances upon hydrolysis. The word carbohydrate originally
referred to compounds of the general formula Cn(H2O)n. However, only the monosaccharides,
known also as simple sugars follow this formula exactly. Oligosaccharides and
polysaccharides have slightly different general formulas which are based on the
monosaccharide units. Oligosaccharides are formed when a few (Greek oligos)
monosaccharides are linked, and polysaccharides are formed when many (Greek polys)
monosaccharides are bonded together. These carbohydrates are referred to as saccharides
because of their sweet taste (latin, saccharum, meaning sugar).

A. Classification of Carbohydrates According to Degree of Complexity

a. Monosaccharides : glucose, fructose, mannose, galactose

b. Disaccharides: sucrose, maltose, cellobiose

c. Oligosaccharides: raffinose

d. Polysaccharides: : starch, cellulose, glycogen

Monosaccharides and disaccharides are called simple carbohydrates, and the

oligosaccharides (2-10 sugar units) and polysaccharides (>10 sugar units) as complex
carbohydrates.

1. Monosaccharide
• carbohydrate that cannot be hydrolyzed to a simpler carbohydrate

• general formula Cn(H2O)n, where n varies from 3 to 8

• maybe an aldose, if containing an aldehyde group or a ketose, if containing a

ketone group

• water soluble, white, crystalline solids

• classified according to the number of carbon atoms: triose (3C); tetrose (4C),
pentose (5C), hexose (6C), and heptose (7C).

• hexoses are the most common of all monosaccharides

Common Monosaccharides

1. Glucose
- blood sugar

- dextrose, grape sugar

- most abundant monosaccharide in the body

- provides a source of energy (ATP) to cells

- from starch, legumes, cereal roots, animal tissues, liver

- converted to other compounds in the body, i.e. glucose can be converted to some
amino acids and fat for long term energy storage; stored as glycogen

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Module on Carbohydrates
CHEM41 and 43 Lecture Course Guide
Department of Physical Sciences and Mathematics

College of Arts and Sciences, University of the Philippines Manila

2. Fructose
- levulose

- sweetest monosaccharide

- converted to glucose and used as energy source

- naturally occurring monosaccharide; found primarily in honey, fruits and vegetables

3. Galactose
- converted to glucose and used as energy source

- components of glycolipids and glycoproteins

- coupled with glucose to make lactose (milk sugar)

4. Mannose
- converted to glucose in the body

- found in certain bacteria, fungi and plant

- used for treating carbohydrate-deficient glycoprotein syndrome, an inherited

metabolic disorder.

Relative Sweetness:

Sucrose = 100
Galactose = 32
Invert sugar = 126

Glucose = 74
Lactose = 16

Fructose = 174
Maltose = 32

Convention of Representing Carbohydrates

1. Fischer Projection

This convention is commonly used for representing open chain forms of carbohydrates.
The carbon chain is vertical with the lowest numbered carbon at the top. Numbering follows
the convention that the most oxidized end of the molecule has the lowest number.

Common monosaccharides, like glucose, mannose, galactose and fructose follow the
same formula, C6H12O6. However, they differ in their configuration or in their functional
group. For example, glucose exists in two forms, D- glucose and L-glucose, the most
naturally occurring of which is the D- isomer (common isomer for most naturally occurring
monosaccharides). Glucose and fructose differ in the functional groups, glucose is an
aldose and fructose is a ketose, thus, are functional isomers. The number of stereoisomers
for a 6-C aldose which have 4 asymmetric centers is given by the formula, 2n, where n is
the number of asymmetric centers. Thus, there are 16 possible sugar stereoisomers (8 D-
sugars and 8 L-sugars).

A comparison of the structures of D-glucose, L-glucose and D-fructose is shown in

Figure 1. The D- and L- prefixes denote the position of the hydroxyl group attached to the
highest-numbered chiral carbon ( the asymmetric C farthest from the aldehyde or keto
group): D-, if OH is on the right side, and L- , if OH is on the left side.

Terminologies to Remember about Stereochemistry of Carbohydrates

• Enantiomers : mirror image molecules (D- and L-sugars are enantiomers)

• Diastereomers : non-superimposable; non-mirror image (e.g. galactose and

mannose)

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Module on Carbohydrates
CHEM41 and 43 Lecture Course Guide
Department of Physical Sciences and Mathematics

College of Arts and Sciences, University of the Philippines Manila

Figure 1. Comparison of the structures of D- and L-

glucose and D-fructose.

• Epimers : differ in arrangement about one other chiral carbons (e.g. glucose and
mannose )

D-glucose and D-mannose (shown below) are not superimposable on each other, and
neither are they mirror images of each other. Such non-superimposable, non-mirror
stereoisomers are called diastereomers. Diastereomers that differ from each other in the
configuration at only one chiral carbon are called epimers.

Figure 2. D-galactose and D-mannose as epimers of D-glucose

D-glucose and D-mannose are examples of these diastereomers, that are called
epimers. D-mannose and D-galactose are non-superimposable, and differ in the
configuration of two chiral carbons; therefore, they are diastereomers that are not epimers.
See Figures 3 and 4 for the complete list of D-monosaccharides in Fischer projection.

2. Haworth Projection

The Haworth representation is an attempt at a more realistic representation of the ring

forms of the sugars in which the placement of substituent can be shown with respect to the
plane of the paper with C-2 and C-3 nearest the observer. The substituents are positioned
above and below this plane.

Like glucose, other sugars with five or six carbon atoms normally exist as cyclic
molecules rather than in the open-chain form. The cyclization takes place as a result of
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Module on Carbohydrates
CHEM41 and 43 Lecture Course Guide
Department of Physical Sciences and Mathematics

College of Arts and Sciences, University of the Philippines Manila

Figure 3. Structures of aldoses.

Figure 4. Structures of ketoses.

interaction between the functional groups on distant carbons, such as C-1 and C-5 (in
aldohexoses, e.g. glucose) to form a cyclic hemiacetal, and between C-2 and C-5 (in
ketohexoses, e.g. fructose) to form a cyclic hemiketal. In either case, the carbonyl carbon
becomes a new chiral center called the anomeric carbon.

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Module on Carbohydrates
CHEM41 and 43 Lecture Course Guide
Department of Physical Sciences and Mathematics

College of Arts and Sciences, University of the Philippines Manila

Cyclization of glucose produces a new asymmetric center at C1. The 2 stereoisomers

formed, ⍺- and β- are called anomers. The designation β- means that -OH on the anomeric
carbon is cis to the terminal -CH2OH; ⍺- means that it is trans. The Haworth structures of
the - and -anomers of glucose are shown below, as well as the Fischer formulas for
comparison.

Figure 5. Cyclization reaction of glucose forming pyranose rings. Adapted from Lehninger Principles of
Biochemistry (4th ed) by Nelson, D.L. & Cox, M.M. (2004).

Cyclization of fructose produces a new asymmetric center at C2, and two

stereoisomers, ⍺- and β-anomers are formed. The Haworth structure of the -anomer (with
-OH group at C2 trans to the terminal -CH2OH) is shown below:

Figure 6. Cyclization of D-fructose form ⍺-D-Fructofuranose

Comparison of the Fischer and Haworth Structures of Glucose and Fructose

In the conversion from Fischer to Haworth, the groups oriented to the right in Fischer
representations are set downwards in Haworth structures. Refer to Figure 7.

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Module on Carbohydrates
CHEM41 and 43 Lecture Course Guide
Department of Physical Sciences and Mathematics

College of Arts and Sciences, University of the Philippines Manila

Figure 7. Comparison of the Fischer and Haworth Projections.

3. Conformational Structures

Haworth projection is often used as a simple representation of the ring forms of the
sugars. However, because the bonds in sugars are single bonds that are flexible, the cyclic
sugars can assume different conformations. For example, cyclic glucose can twist into
alternative conformations called boat and chair conformations, or other orientations in
between. These structures of common hexoses are based on computations of bond angles
and orientation. The substituents are placed relative to a plane denoted by 4 atoms in the
ring. Orientations of these substituents are either axial, i.e. perpendicular to the plane, or
equatorial, i.e. parallel to the plane. Other orientations are in between these two and
denoted quasi-axial or quasi-equatorial. The conformations of five-membered rings,
however, are limited to two, envelope (E) and twist (T). The envelope conformation has four
atoms in a plane while the twist form only has three. In  the  pyranose system,
five conformers are possible: chair (C), boat (B), skew (S), half-chair (H) or envelope (E). In
all cases  there  are four or more atoms that make up a plane. For more information on
conformational analysis of hexoses and pentoses you may visit this link: https://
[Link]/wiki/Carbohydrate_conformation

The conformations are designated as follows (based on rules proposed by the British
Carbohydrate Committee):

1. For six-membered rings, C = chair; B = boat; S or skew = twist boat

2. For five-membered rings, E = envelope, T = twist

3. The pyranoid ring is numbered clockwise starting with the ring oxygen which is
numbered zero.

4. A reference plane is chosen so that it contains four or three of the ring atoms. The
reference plane is chosen so that the lowest numbered carbon atom in the ring is
displaced from the plane

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Module on Carbohydrates
CHEM41 and 43 Lecture Course Guide
Department of Physical Sciences and Mathematics

College of Arts and Sciences, University of the Philippines Manila

5. Ring atoms which lie above the reference plane (numbered clockwise) are written as
superscripts and precede the letter, while ring atoms which lie below the reference
plane are written as subscripts and follow the letter. Example: 4C1 conformation for
glucose, in which C4 of the ring is above the plane, and C1 is below the plane.

Ribose Conformation

The conformations of ribose can be compared with those of the 5-membered

cyclopentane’s envelope and the predominating twisted conformations. These two
conformations, and those of ribose (a sugar in nucleic acids), are illustrated below. Ribose
is the derivative of tetrahydrofuran with 4 atoms in the plane of the envelope form, (Figure
b), and 3 atoms in the twisted conformation (Figure d). The strong electronegativity of
oxygen forces the neighboring carbon atoms to be in one plane. The configurations of
ribose in D- and L-ribose are also shown (Figure c). The twisted cyclic ribose (sugar-pucker
conformation) assumes two dominant forms: (1). C3’-endo major and C2’-exo minor
conformation and (2) C2’-endo major and C3’-exo minor forms found in A- and B-DNA,
respectively (figure d). For details, visit this link, [Link]
10.1089/dna.2019.4943.

Conformations of Pyranoses

The Haworth representation suggests that monosaccharides are flat, but neither
furanose nor pyranose rings are actually planar in their lowest energy confirmations.
Pyranoses like the cyclohexane ring adopt a low-energy conformation that looks like a

Figure 8. Conformations of ribose. Adapted from

[Link]
dna.2019.4943

chair. Because of the tetrahedral nature of carbon bonds, pyranose sugars actually assume
a "chair" or "boat" configuration. The C2-C3-C5-O square forms a plane whereas the C1
and C4 atoms take up a higher or lower position, thus yielding the two possible chairs 1C4
and 4C1. The representation below reflects the chair configuration (4C1) of the
glucopyranose ring more accurately than the Haworth projection. Other possible
conformation of pyranoses are shown in Figure 10.

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Module on Carbohydrates
CHEM41 and 43 Lecture Course Guide
Department of Physical Sciences and Mathematics

College of Arts and Sciences, University of the Philippines Manila

Figure 9. Chair conformations of D-glucose

Figure 10. Other possible conformation for pyranoses.

The relative stabilities of these various conformations depend on the stereochemical

interactions between the substituents on the ring. Close proximity of the flagpole hydrogens
in the boat conformation results in steric strain. This, and the torsional strain associated
with eclipsed bonds at the four carbon atoms that form the side of the boat conformer,
make the boat conformation less stable than the chair conformer. The ring substituents on
the chair conformer fall into two geometrical classes: axial and equatorial. Hydroxyl groups
in pyranoses tend to adopt equatorial position, a conformation that makes hydroxyl groups
farther from each other (depending on the sugar), and minimizes electrostatic repulsions
(repulsions between the electrons of oxygen in the -OH groups). For details, visit this link:
[Link]
than-β-glucose-why-is-glucose-almost-always-α-in-it

Although D-glucose has a strong preference for the 4C1 chair conformation, this is not
true for all monosaccharides. For example, L-iduronic acid (an epimer of glucuronic acid) is
more stable in the 1C4 configuration. In fact, L-iduronic acid is a special case, because the
1C4 configuration is in equilibrium with the so-called skew-boat shape (2So), which favors
the formation of hinges in linear glycan chains. For details, visit this link, https://
[Link]/dam/jcr:00000000-06c2-5b85-0000-00002a863784/[Link]

Supplemental Readings:

Conformations of the Pyranoid Sugars:

- [Link]

- [Link]
β-glucose-why-is-glucose-almost-always-α-in-it

Properties of Monossacharides

1. Optical Activity

As a consequence of its asymmetric center, monosaccharides exhibit optical

activity. The isomer that rotates plane-polarized light in the counterclockwise direction is
termed levorotatory, designated l, or (-), while the isomer that rotates plane-polarized

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Module on Carbohydrates
CHEM41 and 43 Lecture Course Guide
Department of Physical Sciences and Mathematics

College of Arts and Sciences, University of the Philippines Manila

light in the clockwise direction is designated d, or (+), and is dextrorotatory. Optical

activity is used in the sugar industry to measure the sugar concentration of syrup, and
generally in chemistry to measure the concentration or enantiomeric ratio of chiral
molecules in solution.

2. Mutarotation

Mutarotation is the change in optical rotation observed when pure ⍺- or β-anomers

are dissolved in water (or other solvents). Due to ring-chain tautomerism, the ⍺- and β-
anomers slowly interconvert until equilibrium is established. The ⍺-anomer of D-glucose
has a specific rotation of +112.2 degrees in water, and the β-anomer, +18.7 degrees.
When either anomer is dissolved in water,  the value of the specific rotation changes
over time, eventually reaching the same value of +52.5°. This behavior is called
mutarotation (literally means, “change in rotation).

Figure 11. Specific rotations of the different forms of D-glucose.

At equilibrium, the aqueous solution of glucose is consists of 36% ⍺-D-glucose,

64% β-D-glucose, and traces of the linear form. See Figure 12 for details.

Figure 12. Interconversion between the ⍺- and β-anomers of D-glucose. Adapted from https://
[Link]/2017/08/17/mutarotation/

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Module on Carbohydrates
CHEM41 and 43 Lecture Course Guide
Department of Physical Sciences and Mathematics

College of Arts and Sciences, University of the Philippines Manila

3. Oxidation

A. Oxidation of Monosaccharides

Monosaccharides in solution have small amounts of the open chain form present
which can be oxidized to carboxylic acid by oxidizing agent such as Benedict’s. The
oxidation is due to the presence of aldehyde group. Oxidation at C-1 produces aldonic
acid. This reaction is the basis of Benedict’s, Barfoed’s, and Seliwanoff’s tests. The
brick red precipitate formed, which is cuprous oxide (Cu2O) is due to the reduction of
Cu2+ to Cu+ by the sugar, thus, the sugar is called reducing agent.

Figure 13. Oxidation reactions with weak oxidizing agents.

Oxidation of the hydroxymethyl group (C-6 in hexoses), results in the formation of

uronic acids, e.g. glucose glucuronic acid; galactose galacturonic acid. Uronic acids
are biologically important active substances found in mucins and other
glycosaminoglycans.

Figure 14. Formation of Glucuronic acid via enzymatic oxidation.

Other aldohexoses are also oxidized by HNO3, but the aldaric acids products are
soluble in water. Refer to Figure 15. Oxidation of a cyclic hemiacetal gives a lactone.
Refer to Figure 16.

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Module on Carbohydrates
CHEM41 and 43 Lecture Course Guide
Department of Physical Sciences and Mathematics

College of Arts and Sciences, University of the Philippines Manila

Figure 15. Formation of glucaric acid.

Figure 16. Lactone formation from the oxidation of a cyclic hemiacetal.

B. Oxidation of Disaccharides

Compared with monosaccharides, disaccharides are generally much weaker

reducing agents due to the presence of non-reducing component (sugar component
with anomeric carbon involved in glycosidic linkage). 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. Shown below is a disaccharide with a
non-reducing monosaccharide (left monosaccharide) and reducing end (right
monosaccharide). The reducing end has a potential aldehyde group. The ring can open
to yield free C=O at anomeric carbon.

Figure 17. Reducing vs. non-reducing ends.

Because most polysaccharides, e.g. starch, glycogen and cellulose have only one
reducing end (the rest of the monosaccharide components are linked in glycosidic
bonds), they do not have the ability to reduce the oxidizing agents added to them.

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Module on Carbohydrates
CHEM41 and 43 Lecture Course Guide
Department of Physical Sciences and Mathematics

College of Arts and Sciences, University of the Philippines Manila

4. Reduction

The carbonyl group of a monosaccharide can be reduced to an hydroxyl group by a

variety of reducing agents, such as NaBH4, and H2 in the presence of a metal catalyst.
Reduction of the C=O group of a monosaccharide gives a polyhydroxy compound called an
alditol (sugar alcohol). For more details visit this link: [Link]
chemistry/monosaccharides-reduction-alditols/12033/learn/14210

Reduction of D-fructose with sodium borohydride yields a mixture of two alditols due to
C2 racemization.. One of these isomers has the same configuration as the alditol of
glucose, glucitol. The other is the same as the alditol of mannose, mannitol.

Figure 18. Reduction of D-fructose forming D-glucitol and D-

mannitol.

Reduction of aldoses produces only one alditol, e.g. glucose to glucitol (sorbitol) with
NaBH4.

Figure 19. Reduction of D-glucose forming

sorbitol.

Alditols are linear molecules that cannot cyclize in the manner of aldoses. Sugar
alcohols such as sorbitol, D-xylitol and D-mannitol are used as sweeteners in many sugar-
free products such as diet drinks and sugarless gums.

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Module on Carbohydrates
CHEM41 and 43 Lecture Course Guide
Department of Physical Sciences and Mathematics

College of Arts and Sciences, University of the Philippines Manila

5. Exhaustive Methylation

The reaction with alcohols affects only the anomeric carbon. The other hydroxyl groups,
however, can also be methylated using dimethyl sulfate or excess methyl iodide. The
addition of methyl (CH3-) to all the free hydroxyl groups found in the sugar is called
exhaustive methylation, a technique used to determine glycosidic linkages, and the
component monosaccharides. Exhaustive methylation of trehalose (systematic name, ⍺-D-
glucopyranosyl-⍺-D-glucopyranoside) using dimethyl sulfate followed by hydrolysis gives
equimolar amount of 2,3,4,6-tetra-O-methyl-D-glucopyranose.

Figure 20. Exhaustive methylation of trehalose. Adapted from [Link]

trehalose-is-a-disaccharide-that-can-be-obtained-from-fungi-sea-urchins-and-insects.-acid-hydrolysis/
f0866d0d-2017-4856-ba42-bce4cc255c28

6. Formation of Derivatives

A. Esterification: Reaction due to alcohol group

Phosphoric esters are particularly important in the metabolism of sugars to provide

energy. The first step in the utilization of glucose as source of energy is
phosphorylation to glucose-6-phosphate. Phosphorylation involves transfer of a
phosphate group from ATP as shown below:

Figure 21. Formation of a phosphoric ester. Adapted from Biochemistry (7th ed) by Campbell, M.K. &
Farrell, S.O. (2012).

B. Glycoside Formation

A glycoside is a carbohydrate in which the -OH of the anomeric carbon is replaced

by -OR; those derived from furanoses are furanosides; and those from pyranoses are

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Module on Carbohydrates
CHEM41 and 43 Lecture Course Guide
Department of Physical Sciences and Mathematics

College of Arts and Sciences, University of the Philippines Manila

pyranosides. In the following reaction (See Figure 22), methanol reacts with the
anomeric OH on glucose to form methyl glucoside (methyl-⍺-D-glucopyranose).

Figure 22. Glycoside formation. Adapted from Biochemistry (7th ed) by

Campbell, M.K. & Farrell, S.O. (2012).

Carbohydrate acetals, are generally called glycosides.

- acetal of glucose ⟶ glucoside

- acetal of mannose ⟶ mannoside

- ketal of fructose ⟶ fructoside

A hemiacetal or hemiketal can react with non-carbohydrate unit such as alcohol,

glycerol, a sterol or a phenol to give a glycoside. The absence of aldehyde group or
potential aldehyde group (e.g. methyl-⍺-D-glucopyranose) makes glycosides non-
reducing, and therefore cannot react with the oxidizing agents such as Tollen’s,
Benedict’s, and Fehling’s reagents. In acidic solutions, glycosides undergo hydrolysis to
produce sugar and alcohol.

C. Formation of Amino Sugars

In an amino sugar, like glucosamine, an amino group substitutes for a hydroxyl

commonly attached to C-2. In some amino sugars, the amino group is acetylated.
Amino sugars are frequently found in glycoproteins found in the cell membrane, and
proteoglycans.

Figure 23. Structures of glucosamine and N-

acetylglucosamine.

Other examples of amino sugars are shown in Figure 24.:

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Module on Carbohydrates
CHEM41 and 43 Lecture Course Guide
Department of Physical Sciences and Mathematics

College of Arts and Sciences, University of the Philippines Manila

Figure 24. Other examples of amino sugars.

D. Formation of Sugar Sulfates

Some polysaccharides contain monosaccharide units with sulfates, at C-2, C-4 and/
or C-6. These polysaccharides are found mostly in the proteoglycans of the extracellular
matrix. These include chondroitin sulfates, keratin sulfates, dermatan sulfates and
heparin. The sulfate groups which are negatively charged at physiological pH impart
negative charge to these compounds.

Figure 25. Structure of Chondroitin-4-sulfate. Adapted from

Lehninger Principles of Biochemistry (4th ed) by Nelson, D.L. &
Cox, M.M. (2004).

E. Formation of N-acetylneuraminate

N-acetylneuraminic acid, also called sialic acid is often found as a terminal residue
of oligosaccharide chains of glycoproteins. Sialic acid imparts negative charge to
glycoproteins, because its carboxyl group dissociates with a release of proton at
physiological pH.

Figure 26. Structure of N-acetylnueraminate also

known as sialic acid. Page 16 of 33
Module on Carbohydrates
CHEM41 and 43 Lecture Course Guide
Department of Physical Sciences and Mathematics

College of Arts and Sciences, University of the Philippines Manila

2. Disaccharide
How are disaccharides and polysaccharides formed from monosaccharides?

Sugars are readily joined together in cells. Two monosaccharides can react to form a
disaccharide. The anomeric hydroxyl and a hydroxyl of another sugar can join together, with
removal of water to form a glycosidic bond (the bond from the anomeric carbon to the -OR
group). This reaction is also the basis for the formation of polysaccharides and
oligosaccharides.

Figure 27. Formation of glycosidic bond.

The formation of disaccharides and longer saccharides is an example of dehydration (an

elimination) reaction. Some of the disaccharides are repeating units of the high molecular
weight polysaccharides. Common digestible disaccharides include maltose, lactose and
sucrose. Only monosaccharides can be absorbed from the digestive tract into the blood,
therefore these disaccharides must first be digested into their monosaccharide units. In the
small intestine, are specific enzymes for each of these disaccharides: maltase to digest
maltose, lactase to digest lactose, and sucrase to digest sucrose.

Figure 28. Structures of the three most common digestible disaccharides: maltose, lactose,
and sucrose.

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Module on Carbohydrates
CHEM41 and 43 Lecture Course Guide
Department of Physical Sciences and Mathematics

College of Arts and Sciences, University of the Philippines Manila

Below in Table 1 is a comparison of the characteristics of the three common

disaccharides:

Table 1. Comparison of the three common disaccharides.

Name Composition Characteristics

Maltose Glucose + Glucose Found in germinating seeds, and beer

Lactose Glucose + Galactose Milk sugar; found in dairy products

Table sugar; most common dietary disaccharide;

Sucrose Glucose + Fructose naturally found in beet and cane sugar, brown sugar,
and honey

Glycosidic linkages can take various forms; the anomeric carbon of one sugar to any of
the -OH groups of another sugar to form an ⍺- or β-glycosidic linkage. Shown below are
three of the many disaccharides that can be formed from two glucose molecules.

Figure 29. Various forms of glycosidic linkages.

3. Polysaccharide
Carbohydrates exist in nature mostly as polysaccharides, such as cellulose, chitin,
glycogen, starch, and hyaluronic acid. These compounds are high molecular weight

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Module on Carbohydrates
CHEM41 and 43 Lecture Course Guide
Department of Physical Sciences and Mathematics

College of Arts and Sciences, University of the Philippines Manila

polymers composed of monosaccharide- or disaccharide-repeating units linked together by

glycosidic bonds. The  main functions  of  polysaccharides  are structural support, energy
storage, and cellular communication.

Classification:

I. Homoglycans – homopolysaccharides containing only one type of

monosaccharide, e.g. Glucans – polymer containing glucoses

II. Heteroglycans – heteropolysaccharides containing residues of more than one type

of monosaccharide.

Glucans are polysaccharides made up of glucose as the only monosaccharide

constituent, e.g. amylose and amylopectin (components of starch), glycogen, dextran and
cellulose. Other classes of homopolysaccharides are the homopolyaminosaccharides such
as chitin and homopolyuronosaccharides which include alginic and pectin.

The mucopolysaccharides or glycosaminoglycans and glycosaminoglucuronoglycans

are examples of heteropolysaccharides. These substances are found in connective tissues,
bacterial cell walls, eyeball synovial fluids, cornea and in the circulatory system in humans.
The most abundant of the mucopolysaccharides are hyaluronic acid, chondroitin sulfates,
keratin sulfates, dermatan sulfates and heparin.

I. Homopolysaccharides
A. Storage Polysaccharide
Organisms store carbohydrates in the form of polysaccharides, to lower the osmotic
pressure. Since osmotic pressure depends on the number of molecules, the osmotic
pressure is greatly reduced by formation of a few polysaccharide molecules.

1. Starch
Starch is the most important source of carbohydrate in the human diet and accounts
for more than 50% of our carbohydrate intake. Plants are able to synthesize glucose
using light energy gathered in photosynthesis, and the excess glucose beyond the
plant’s immediate energy needs, is stored as starch in different plant parts, including
roots and seeds. Starch is stored in globular structures called starch granules. It
consists of two types of polysaccharides: amylose (10-30%) and amylopectin (70-90%).
Both polymers are consist of -D-glucose units in the 4C1 conformation.

a. Amylose
- linear chain of D-glucose in (14) linkages; adopts helical conformation

- its repeating disaccharide unit is maltose (D-glucopyranosyl α(1→4)-D-

glucopyranoside.

Figure 30. Repeating structure of amylose.

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Figure 30. Spiral structure of amylose. Adapted from [Link]

Courses/Sacramento_City_College/SCC%3A_Chem_309_-
_General_Organic_and_Biochemistry_(Bennett)/Text/14%3A_Carbohydrates/
14.7%3A_Polysaccharides.

Amylose adopts a helical conformation with 6 glucose units per turn, stabilized by
hydrogen bonding. When coiled, it can accommodate iodine molecule that gives
characteristic blue-violet color. The blue-violet color is due to the formation of amylose-
iodine complex. This color test is sensitive enough to detect even minute amounts of
starch in solution.

b. Amylopectin
- component of starch, other than amylose

- highly branched chain of glucose units; with (1→4) and (1→6) linkages shown
below:

Figure 31. Repeating structure of amylopectin.

Amylopectin molecule may contain many thousands of glucose units with branch
points occurring about every 25-30 units. This branching is determined by branching
enzymes which leave each chain with up to 30 glucose residues. Due to branching, the
helical structure of amylopectin is disrupted, so instead of the deep blue-violet color
amylose gives with iodine, amylopectin produces a less intense reddish brown.

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Partial hydrolysis of starch produces polysaccharides of intermediate sizes, called

dextrins. Dextrins have characteristic stickiness when wet, that is why they are used as
adhesives, as binders to hold pills and tablets together, and as pastes. They are more
easily digested than starch and are therefore used extensively in the commercial
preparation of infant foods. The complete hydrolysis of starch yields, in successive
stages, glucose:

starch → dextrins → maltose → glucose

In the human body, several enzymes known collectively as amylases degrade starch
sequentially into usable glucose units.

2. Glycogen
Glycogen is the storage form of glucose in animals. In humans, glycogen is made
from excess glucose and stored primarily in the cells of the liver and skeletal muscle. It
has a structure similar to  amylopectin, but is more extensively branched (with more
⍺(1⟶6) linkages), and compact than starch. Its highly branched structure permits rapid
glucose release especially when glucose availability is limiting. e.g., in muscle during
exercise. Glycogen is found in the form of granules in the cytoplasm in many cell types.
It exists in cells as spherical or globular structure. The structure of glycogen and the two
types of linkages are shown below:

Schematic two-dimensional cross-

sectional view of glycogen: a core
protein of glycogenin is surrounded
by vranches of glucose units. The
entire globular granule may contain
around 30,000 glucose units.

Figure 32. Repeating structure of glycogen (top). Cross-sectional view of glycogen (bottom), adapted from
Haggstrom, M. (2014). Glycogen structure. WikiJournal of Medicine, 1(2), 8. Page 21 of 33
Module on Carbohydrates
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Laboratory Activity: Experiment 7: Isolation of Glycogen from Chicken Liver

B. Structural Polysaccharide
1. Cellulose
Cellulose, a major structural component of plant cell walls is consists of long linear
chains of glucose joined in β(1⟶4) linkages. The glucose units in cellulose are linked in
a linear fashion, as shown in the drawing below.

Figure 33. Repeating structure of cellulose.

The beta-glycoside bonds permit these chains to stretch out, and this conformation
is stabilized by intramolecular hydrogen bonds. A parallel orientation of adjacent chains
is also favored by intermolecular hydrogen bonds. Stability is achieved by having each
glucose unit flipped or rotated 1800 relative to the preceding and succeeding
monosaccharide unit. The result is almost fully extended molecule. For the arrangement
of fibrils, microfibrils, and cellulose in cell walls, visit this link, [Link]
[Link]/2013/06/[Link].

Molecular Structure of Cellulose

In the cellulose chain, the glucose units are in 6-membered rings, called pyranoses.
They are joined by single oxygen atoms (acetal linkages) between the C1 of one
pyranose ring and the C-4 of the next ring. The spatial arrangement, or stereochemistry,
of these acetal linkages is very important. The pyranose rings of the cellulose molecule
have all of the groups larger than hydrogen sticking out from the periphery of the rings
(equatorial positions). The stereochemistry at carbons 2,3,4 and 5 of the glucose
molecule are fixed; but when glucose forms a pyranose ring, the hydroxyl at C-4 can
approach the carbonyl at C-1 from either side, resulting in two different conformations
at C-1.

In plant cell walls, approximately 36 individual cellulose molecule chains connect

with each other through hydrogen bonding to form larger units known as elementary
fibrils, which are packed into larger microfibrils with 5-50 nm in diameter and several
micrometers in length ([Link]
characterization-and-applications/recent-development-in-applications-of-cellulose-
nanocrystals-for-advanced-polymer-based-nanocomposit). These microfibrils have
disordered (amorphous) regions and highly ordered (crystalline) regions as shown in the
illustration below. In the crystalline regions, cellulose chains are closely packed together
by a strong and highly intricate intra- and intermolecular hydrogen-bond network , while
the amorphous domains are loosely packed. The alternate flipping of glucose in the
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cellulose molecule promotes these intra-chain and inter-chain H-bonds and van der
Waals interactions among cellulose molecules, and this explains why cellulose chains
are straight and rigid, and packed well in a crystalline arrangement in thick bundles,
called microfibrils. When subjected to mechanical shearing and treatment with
chemicals or enzymes, the loose amorphous regions of cellulose microfibrils are
selectively hydrolyzed because they are more susceptible to be attacked in contrast to
crystalline regions.

The two distinct regions in cellulose, crystalline and amorphous are differentiated below:

Figure 34. Amorphous and crystalline regions in celllulose microfibrils. Adapted from https://
[Link]/books/nanocrystals-synthesis-characterization-and-applications/
recent-development-in-applications-of-cellulose-nanocrystals-for-advanced-polymer-
based-nanocomposit

Cellulose – Not a Human Nutrient

Enzymes that hydrolyze ⍺-linkages in starch cannot hydrolyze the β-linkages in

cellulose. Only a few organisms possess cellulase, the enzyme that hydrolyzes β(1⟶4)
linkages in cellulose. Ruminants (cows, goats) and termites have within their digestive
tracts microorganisms that produce cellulase. All wood fungi, likewise, have cellulase.
Since human’s digestive juices lack the enzyme cellulase, cellulose cannot be digested
and absorbed. Cellulose simply passes through the digestive tract as insoluble fiber.
The cellulose fiber, however, functions by: facilitating the smooth passage of food
through the digestive tract by stimulating mucus secretion; decreasing absorption of
glucose and cholesterol; by increasing the bulk of stool, thus, preventing constipation.

2. Chitin
Chitin is the major structural component of the exoskeletons of invertebrates, such
as insects and crustaceans. It also occurs in cell walls of algae, fungi, and yeasts. This
earth’s second most abundant carbohydrate polymer (after cellulose) is composed of
units of N-acetyl-β-D-glucosamine joined by -1,4-glycosidic bonds. The repeating unit
is shown in Figure [Link] structural feature of chitin is similar to that of cellulose, but
the hydroxyl group at C-2 of its glucoses is replaced by an acetylamido group.

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Figure 35. Repeating structure of chitin.

Chitin-based coatings can extend the shelf life of fruits. It is also used to make a
strong and flexible surgical thread that decomposes after the wound or incision heals.

3. Alginic acid

Alginic acid is a linear polymer made up of D-mannuronic acid, joined by β-1⟶4

linkages. It is the main structural polysaccharide of brown algae, and is used mainly as a
food additive.

C. Other homopolysaccharides
1. Pectic acid (a homopolyuronosaccharide)
This polygalacturonan polysaccharide occurs mainly in cell walls and intercellular
layers of all plant tissues. It is a linear structure made up of galacturonic acid linked in
⍺(1⟶4) bonds.

2. Dextran

Dextran is a group of glucans made up of glucose units joined in ⍺(1⟶6) with cross
linkages. It is produced by lactic acid bacteria (Lactobacillaceae) from sucrose. It is
used as food additive or as a matrix in protein separation technique such as gel filtration
chromatography. In the oral cavity, dextran forms a net-like structure that forms the
matrix for plaques. The structure favors bacterial aggregation that produces acids
destroying the enamel of teeth.

3. Inulin

Inulin is a polymer of D-fructose (fructosans), joined in β(1⟶2) glycosidic linkage. It

occurs in bulbs of onion and garlic, but not utilized by the body. Instead, it is used for
assessing kidney function through measurement of glomerular filtration rate (GFR).

II. Heteropolysaccharide
A. Glycosaminoglycan
Glycosaminoglycans or mucopolysaccharides are long linear polysaccharides
consisting of repeating disaccharides in which one of the monosaccharide units is an amino
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sugar and one (or both) of the monosaccharide units contains at least one negatively
charged sulfate or carboxyl group (e.g. D-glucuronic). The amino sugar is always either N-
acetylglucosamine or N-acetylgalactosamine. In some glycosaminoglycans, one or more of
the hydroxyls of the amino sugar are esterified with sulfate.

The glycosaminoglycans are the main constituents of the mucins, connective tissues
and the extracellular matrix. They are normally found linked with proteins as a proteoglycan
structure. The structures of the repeating disaccharide units of glycosaminoglycans are
shown below:

Figure 36. Structures of glycosaminoglycans. Adapted from Lehninger Principles of Biochemistry (4th ed)
by Nelson, D.L. & Cox, M.M. (2004).

1. Hyaluronic acid
• contains alternating residues of D-glucuronic acid and N-acetylglucosamine,
joined in β(1⟶3) & β(1⟶4) glycosidic lnkages.

• forms clear, highly viscous solution that serves as lubricants in the synovial fluid
of joints and give the vitreous humor of the vertebrate eye its jelly-like consistency

• an essential component of the extracellular matrix of cartilage and tendons;

contributes to their tensile strength and elasticity

• Consist of as many as 25,000 disaccharide units, with molecular weights of up to

107

2. Heparin
• has the highest net negative charge of the glycosaminoglycans shown above.

• a natural anticoagulant substance.

• binds strongly to antithrombin III (a protein involved in terminating the clotting

process) and inhibits blood clotting.

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3. Chondroitins and keratan sulfate

• found in tendons, cartilage, and other connective tissue

4. Dermatan sulfate
• As its name implies, is a component of the extracellular matrix of skin

B. Proteoglycans
Proteoglycans are macromolecules on the cell surface or extracellular matrix in which
one or more glycosaminoglycan chains ((≈95%) are joined covalently to a membrane
protein or a secreted protein.

They serve the following functions: act as lubricants; give tensile strength and elasticity
to soft tissues; act as shock absorber of hard and brittle structures, such as bone; provide
passageways in extracellular matrix; and help in disposing of unwanted cellular artifacts as
well as pathogens.

Figure 37. Structure of a proteoglycan from an integral protein (left). Proteoglycan structure from the extracellular
matrix (right). Adapted from Lehninger Principles of Biochemistry (4th ed) by Nelson, D.L. & Cox, M.M. (2004).

The above structure is a very flexible or loose structure due to the fact that covalent
linkage is only between proteins and the mucopolysaccharides. The mucopolysaccharides
are autonomous of each other, interacting only via noncovalent bonds. These are weaker
interactions that can readily form, break, then reform again. Thus, because the interactions
are weak, the molecules are allowed to expand to variable sizes. When water binds to the
hydroxyl, sulfates and carboxyl groups, the structure increases in size several fold,
sometimes reaching 500X its original size. Because mucopolysaccharides are heavily
negatively charged due to the presence of sulfates and carboxyl groups, they could easily
bind positively charged groups in proteins. Membrane proteins and surface antigens in
viruses and bacteria, as well as hydrolytic products of antigen-processing T cells (APC) can

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therefore interact with the mucopolysaccharides facilitating their expulsion from tissues. It is
thus one of the host’s responses and defense to infection.

Below is a proteoglycan structure that shows the trisaccharide bridge, a typical

trisaccharide linker (blue) that connects a glycosaminoglycan (e.g. chondroitin sulfate) to a
serine residue (pink) in the core protein. The xylose residue at the reducing end of the linker
is joined by its anomeric carbon to the hydroxyl of serine residue. In proteoglycans, as well
as glycoproteins, the sugars are attached to proteins via serine or threonine, and to a lesser
extent, tyrosine (O-linked), or lysine, asparagine and glutamine (N-linked)

Figure 38. Trisaccharide bridge in a proteoglycan. Adapted from

Lehninger Principles of Biochemistry (4th ed) by Nelson, D.L. &
Cox, M.M. (2004).

C. Peptidoglycans
Bacteria use cell wall to protect their cellular contents. Cell wall helps by providing
protection from osmotic lysis, toxic chemicals, and pathogens. Normally, bacteria exhibit
high internal osmotic pressures, and frequently encounter variable, often hypotonic exterior
conditions that lead to their swelling. Swelling is prevented (or in some cases shrinkage due
to variations in solution osmotic strength) through their rigid cell walls.

Peptidoglycans are the major components of bacterial cell wall. They are peptide joined
heteroglycan chains composed of alternating GlcNAc and N-acetylmuramic acid (MurNAc)
connected by β-1,4 linkages.

The peptide subunits usually contain four alternating L- and D-amino acids, connected
to the glycan stands via the lactyl groups of the N-acetylmuramic acid residues. Cross-
linking of the glycan strands generally occurs between the carboxyl group of D-Ala at
position 4 and the amino group of the lysine at position 3, either directly or through a short
peptide bridge. The GlcNAc (β-1⟶4) MurNAc strands are covalently connected by a
pentaglycine bridge through the epsilon amino group of the tetrapeptide Lys on one strand
and the D-Ala of a tetrapeptide on another strand. Below is a pictorial presentation of
peptidoglycan structure.

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Figure 39. Structure of a typical peptidoglycan. https://

[Link]/content/105/30/10348/tab-figures-data

Figure 40. Pictorial representation of the peptidoglycan structure. https://

[Link]/services/peptidoglycan-structure-
[Link]

Gram (+) bacteria have a thick cell wall, approximately 2 nm, with multiple layers of
peptidoglycan, surrounding the bacterial plasma membrane, whereas, Gram (-) bacteria
have a thin cell wall, consisting of single layer of peptidoglycan sandwiched between the
inner and outer lipid bilayer membranes. Below is a comparison of the cell envelopes of
gram-positive and gram-negative bacteria.

Figure 41. Structures of the cell walls of Gram (+) and Gram (-) bacteria.
Adapted from CNX OpenStax/Wikimedia Commons/CC BY-SA 4.0

The peptidoglycan layer is responsible for reacting with crystal violet giving the
characteristic blue violet color with gram stain of gram (+) bacteria. Gram (-) bacteria have a
protective lipopolysaccharide layer which does not dissolve hydrophilic dyes such as
crystal violet, thus, preventing it from interacting with the peptidoglycan layer of the
bacterial cell wall.

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The peptidoglycan layers of many gram-positive bacteria are densely functionalized

with anionic glycopolymers called wall teichoic acids (WTAs). Teichoic acid is often attached
to the C6 of MurNAc. It is a polymer of glycerol or ribitol to which alternative GlcNAc and D-
Ala are linked to the middle C of the glycerol. Multiple glycerols are linked through
phosphodiester bonds. Teichoic acids often make up 50% of the dry weight of the cell wall,
and present a foreign (or antigenic) surface to infected hosts. These often serve as
receptors for viruses that infect bacteria (called bacteriophages). Below is the structure of
teichoic acid.

Figure 42. Representative chemical structure of wall teichoic acids. Adapted from Swoboda, J. G., Campbell, J.,
Meredith, T. C., & Walker, S. (2010). Wall teichoic acid function, biosynthesis, and
inhibition. Chembiochem, 11(1), 35-45.

Figure 43. Structure of bacterial lipopolysaccharides.

Adapted from Lehninger Principles of Biochemistry (4th
ed) by Nelson, D.L. & Cox, M.M. (2004). Page 29 of 33
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D. Lipopolysaccharide in the Outer Membrane of Gram-negative Bacteria

The outer membrane of Gram (-) bacteria is consists of a lipid group (anchored in the
outer membrane) joined to a polysaccharide made up of long chains with many different
and characteristic repeating structures. These many different unique units determine the
antigenicity of the bacteria; that is, animal immune systems recognize them as foreign
substances and raise antibodies against them. As a group, these antigenic determinants
are called the O antigens. See Figure 43.

E. Glycoproteins
Glycoproteins contain carbohydrate residues in addition to the polypeptide chain. Some
of the most important examples of glycoproteins are involved in the immune response, for
example, antibodies, which bind to and immobilize antigens (the substances attacking the
organism). Carbohydrates also play an important role as antigenic determinants, e.g. blood
group antigenic determinants, A and B. Known glycoproteins also include structural
proteins, enzymes, membrane receptors, and transport proteins.

The oligosaccharide components of glycoproteins exhibit great variability in sugar

sequence and composition. Proteins with identical amino acid sequence but different
oligosaccharide composition are called glycoforms. In cell membranes, glycoproteins are
concentrated mainly at the outer half of the membrane bilayer where they comprise the
glycocalyx of the cell.

Glycosylation can affect the physical and chemical properties of proteins, altering
solubility, mass, and electrical charge. Carbohydrate moieties have been shown to stabilize
protein conformations and protect proteins against proteolysis.

How are the oligosaccharides joined to proteins in the glycoproteins?

The carbohydrate units, mostly N-acetylglucosamine and N-acetylgalactosamine, are

covalently linked to polypeptide chains via the hydroxyl groups of serine, threonine or
hydroxylysine residues (in O-linked saccharides); or via the amide N of Asn (N-linked), as
shown in Figure 44.

Figure 44. O- and N-linkage for protein connections.

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O-linked oligosaccharides have a glycosidic bond to the hydroxyl group of serine (or
threonine) residues. N-linked oligosaccharides have N-glycosyl bond to the amide nitrogen
of asparagine residue.

1. O-linked Saccharides
• Often found in cell surface glycoproteins and in mucins

• Mucins – large glycoproteins that coat and protect mucous membranes in the
respiratory and gastrointestinal tracts in the body

• A unique family of O-linked glycoproteins permits fish to live in the icy seawater of
the Arctic and Antartic regions (-1.90℃)

2. N-linked Saccharides
• Found in many different proteins, including immunoglobulins G and M, ribonuclease
B, ovalbumin and peptide hormones

The Blood Group Antigens

Oligosaccharide portions of glycoproteins act as antigenic determinants. Among the

first antigenic determinants discovered were the blood group substances. In the ABO
system, individuals are classified according to four blood types: A, B, AB, and O. Below are
the structures of blood-group antigenic determinants:

Figure 45. Structures of the ABO blood groups.

At the cellular level, the biochemical basis for specific blood type is a group of relatively
small membrane-bound carbohydrates (oligosaccharides), called blood group antigens,
denoted ABO antigens. These oligosaccharides are found on membrane surfaces of red
blood cells and are either O-linked to proteins or covalently bonded to lipids forming
glycolipids. They elicit an antibody response causing agglutination of the blood of
individuals who do not have the specific oligosaccharide in their erythrocyte membrane. For
example, an individual whose erythrocyte contains the oligosaccharide, denoted A antigen

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CHEM41 and 43 Lecture Course Guide
Department of Physical Sciences and Mathematics

College of Arts and Sciences, University of the Philippines Manila

will elicit an immunologic response to the blood group type B which will not be recognized
as self. Type O antigen will not elicit antibody reaction in individuals with type A and B
surface antigens since the 4-saccharide cluster is common to all three antigens.

Exercises
1. Indicate whether each of the following pairs of sugars consists of anomers, epimers, or an
aldose-ketose pair:

A. D-glyceraldehyde and dihydroxyacetone

B. D-glucose and D-mannose

C. D-glucose and D-fructose

D. ⍺-D-glucose and β-D-glucose

E. D-ribose and D-ribulose

F. D-galactose and D-glucose

2. Draw the open chain and two anomers of D-galactopyranose, and predict the most stable
form. Explain your answer.

3. Identify the following four sugars:

4. Why is mannose most frequently found as ⍺-anomer?

5. How many different oligosaccharides can be made by linking one glucose, one mannose,
and one galactose? Assume that each sugar is in its pyranose form. Compare this number
with the number of tripeptides that can be made from three different amino acids.

6. What structural property of a sugar enables it to reduce oxidizing agents? Based on this
property, determine which of the following are reducing sugars?

A. Ribofuranose
C. Lactose
E. Sucrose

B. Methylglucose
D. Amylose
F. Cellulose 


7. Use the following figure of raffinose to answer the following questions:

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Department of Physical Sciences and Mathematics

College of Arts and Sciences, University of the Philippines Manila

A. Is raffinose a reducing sugar? Explain.

B. What are the monosaccharides that compose raffinose?

C. β-galactosidase is an enzyme that will remove galactose residues from an

oligossaccharide. What are the products of β-galactosidase treatment of raffinose?

8. What products can be formed from exhaustive methylation of the β-anomer of lactose?

9. A trisaccharide obtained from the partial hydrolysis of amylopectin showed two glycosidic
linkages.

A. Draw the structure of the trisaccharide

B. If the trisaccharide is to be exhaustively methylated and subsequently hydrolyzed with

an acid, how many different methylated products will be obtained? Draw their
structures.

C. Can an aqueous solution of the trisaccharide precipitate Cu as Cu2O? If it can, encircle

the potential carbonyl carbon(s) in the trisaccharide.

D. Can the trisaccharide exist in different anomeric forms? If yes, draw their structures.

10. After exhaustive methylation and hydrolysis, a polysaccharide yielded equimolar amounts
of 2,3,4-tri-O-methylglucose and 2,3,6-tri-O-methylglucose. The polysaccharide has one
reducing terminus. Draw the structure of the polysaccharide.

11. Carbohydrates in the membranes are in the form of glycolipids and glycoproteins. Given
the following peptide, attach glucose residues to the peptide shown below:

M-R-V-I-L-S-C-K-R-V-M-C-N-E-H-G-G-A-T-H

12. Discuss the relationship of the structure of each of the following carbohydrates to the
function indicated.

A. Hyaluronic acid is a major component of the synovial fluid which lubricates joints

B. Cellulose is a major component of the rigid cell walls of plants

C. Amylose and amylopectin are storage forms of D-glucose in plants

D. Glycogen is the storage polysaccharide in animal cells

13. Why is type AB blood considered a universal acceptor (i.e. does not elicit antibody reaction
with blood group types A,B, and O?

References:
1. Principles of Biochemistry, Lehninger

2. Biochemistry, Stryer

3. Biochemistry, Campbell and Farrell

4. [Link]

5. [Link]

6. [Link]

7. [Link]

8. [Link]
applications/recent-development-in-applications-of-cellulose-nanocrystals-for-advanced-
polymer-based-nanocomposit

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