Topic 2:

CARBOHYDRATE
CHEMISTRY
ROSALIE E. SOLIVIO
Faculty, CASE – Physical Science Department
Lesson 1
• Introduction to Carbohydrates
• Functions of Carbohydrates
• Classification of Carbohydrates
A. Monosaccharides
B. Disaccharides
C. Oligosaccharides
D. Polysaccharides
• Reaction of Hexoses
• Structures of Carbohydrates (Open-chain & cyclic)
Learning Objectives:

At the end of the lesson, the learners should be able to:

• Define carbohydrates.
• Identify the functional groups in sugars
• State the functions of carbohydrates physiologically .
• Classify carbohydrates based on the number of carbon atoms;
number of monosaccharide present in disaccharides, etc.
• Define related terms: epimers, D & L configuration; penultimate
carbon, chiral carbon, anomeric carbon.
• Write chemical equations undergone by physiologically
important hexoses.
• Write open-chain and cyclic structures of simple sugars.
• Identify monosaccharides in the open-chain(linear) structures
and cyclic structures (Haworth & Chair) .
Can you survive without sugar?
 Carbohydrates (CHO)
• Most abundant organic compound found in nature.
• Constitutes the supporting structure and tissue of
plants.
• Essential in the diet of animals.
• Are formed in a process called photosynthesis.
 Carbohydrates (CHO)
• Made up of sugar units linked by glycosidic
bond.
• Small carbohydrate molecules are referred
to as glycosides.
• Composed of carbon, hydrogen and
oxygen and that the hydrogen to oxygen
ratio is 2:1 just like in water.
• Formerly defined as hydrates of carbon.
 Carbohydrates
• Now defined as polyhydroxy aldehydes or
ketones or compounds that will yield on
hydrolysis, aldehydes or ketones.

• “Saccharide” comes from the word for table

sugar in several language: sarkara n Sanskrit,
sakcharon in Greek, saccharum in Latin.
 • Sugars are prepared by mild oxidation of alcohol.
• Glycerol is a trihydroxy alcohol

D-glyceraldehyde: Functional groups present are –CHO (aldehyde), -OH (hydroxy)

Dihydroxyacetone: Functional groups present are –C=O (ketone), -OH (hydroxy)

Functional Groups in Sugars
 Functions of Carbohydrates
• Oxidation of carbohydrates provides energy.
• Glycogen, a carbohydrate storage provides a short-
term energy reserve.
• Supplies carbon atoms for the synthesis of other
biochemical substances lipids, proteins and nucleic
acids.
• Forms a structural component to cell membrane when
bonded to lipids.
• Part of the structural framework of nucleic acids, DNA
& RNA.
Lesson 2 – Classification of Carbohydrates
Structures of Carbohydrates (Open-
chain & cyclic)
Learning Objectives:
At the end of the lesson, the learners will be able to:
• Classify carbohydrates based on the number of carbon
atoms; number of monosaccharide present in
disaccharides, etc.
• Define related terms: epimers, D & L configuration;
penultimate carbon, chiral carbon, anomeric carbon.
• Write open-chain and cyclic structures of simple sugars.
• Identify monosaccharides in the open-chain(linear)
structures and cyclic structures (Haworth & Chair) .
Classification of Carbohydrates
I. Monosaccharides - are the basic units of
carbohydrates and they cannot be hydrolyzed further.

• Classified according to the number of carbon atoms

present.
A. Trioses – contain 3 C atoms and have a
molecular formula, MF of C3H6O3.
B. Tetroses - contain 4 C atoms, MF is C4H8O4

C. Pentoses – contain 5 C atoms, MF is C5H10O5

D. Hexoses – contain 6 C atoms, MF is C6H12O6.
They are the most important monosaccharides.
1. Aldohexoses - those containing an aldehyde
group.
2. Ketohexoses – contain a ketone group.

The most popular ketohexose is fructose, is the

sweetest natural sugar. D-psicose, D-fructose,
D-tagatose and D-sorbose has a ketone group in
their carbon no. 2
 TRIVIA: Sugars found in nature are D-
configurated.

Asymmetric carbon or chiral carbon a carbon attached to 4 different groups.

(-CHO, -OH, CH2OH, H)
***The asymmetric carbon in glyceraldehyde is also the penultimate carbon.
Penultimate carbon - 2nd from the last carbon.
When –OH is to the right of the penultimate carbon = D-configurated
When –OH is to the left of the penultimate carbon = L-configurated
Penultimate carbon
D-configurated sugars
 Structures of Monosaccharides

• Crystalline monosaccharides are found in open

chain structures.
• When dissolved in water, most of the pentoses &
hexoses are converted into ring structures via
cyclization to form hemi-acetal or hemi-ketal
structures.
• The two ring structures are: furanose and
pyranose.
• Furanose: a 5-membered ring in which 1 oxygen
& 4 carbon atoms are found. Oxygen is linked
with carbons 1 & 4 for ribose & deoxyribose while
carbons 2 & 5 for fructose. All pentoses and
ketohexoses are transformed to furanose ring.

• Pyranose: a 6-membered ring in which 1 oxygen

& 5 carbon atoms are found.
Oxygen is linked with carbons 1 & 5. Only
aldohexoses are transformed into pyranose ring.
Structures of Monosaccharides
In Fisher’s, when –OH is to the
right of the anomeric carbon, it is
in its alpha (α)form while if –OH is
on the left, it is in its beta(β)
form. The name of the ring chain
ribose is now α-D ribose.

H With Haworth’s, when –OH is

OH down in the anomeric carbon, it
O is in its alpha form. The ring
H structure shown is α-D-ribose.
Conversion of open chain ribose to ring chain

•In the cyclization of ribose, -OH of C4 is added to carbonyl grp of C1.

•C1 in Fischer’s is now called an anomeric carbon.
•C1 in Haworth’s is also an anomeric carbon.
 Anomeric carbon

Anomeric carbon- a carbon that becomes asymmetric only when sugar

assumes the hemi-acetal or hemi-ketal structures.
 Cyclization of Glucose

• In the cyclization of glucose, OH of C5 is added to carbonyl grp of C1 to form

alpha and beta anomers as shown above.
•Carbon 1 becomes an anomeric carbon.
Haworth’s structure of glucose

α-D glucose β-D-glucose

Chair conformation of glucose

or α-D-glucose or β-D-glucose
 Cyclization of Fructose

•In the cyclization of fructose, -OH of C5 is added to carbonyl group or C2.

•C2 now is the anomeric carbon of fructose.
•In the Haworth’s projection, when –OH is down in the anomeric carbon(C2)
it is an alpha anomer; if –OH is up in the anomeric carbon then it is a beta
anomer.
Writing structure from Fischer’s Projection to
Haworth’s

• all substituents to the right of

anomeric carbon (C1) in α-D
glucose (Fischer’s) are written
below in the pyranose ring.
• when –OH is down in the
anomeric carbon (C1), the
structure is now named
α-D-glucopyranose or simply
α-D-glucose.
Writing structure from Fischer’s Projection to
Chair Conformation
•Substituents are
attached to the ring
either axially or
equatorially.
=== •Substituents
encircled in red are
attached down the
ring.
•-OH in Carbon 1
(anomeric carbon) is
up or equatorially
Fischer’s Projection attached in the ring
Chair Conformation giving a β-anomer.
 Exercise 1
1. From the given structures below, which Haworth’s structure is β-D-glucose?
a. b.

2. Below is the chair conformation of a. What is its anomeric form?

glucose, answer the following
questions on the other side.
b. How many –OH is/are attached axially?
c. How many –OH is/are attached equatorially?
d. How many –H is/are attached equatorially?
e. How many –H is/are attached axially?
f. What substituents are attached to carbon 5?
g. What carbon atoms connects oxygen (O)
in the ring structure?
h. What is the complete name of the structure?
 FYI
1. Glucose - preferred fuel of the brain; blood
sugar; dextrose; grape sugar
2. mannose – good sources are fruits like
cranberries, veggies like eggplant, cabbage,
legumes, herbs like aloe vera.
3. galactose – sugar w/c is less sweet than glu and
fru; commonly occurring in lactose and in
certain pectin, gums & mucilage.
4. Fructose – sweetest sugar; fruit sugar; levulose
 Practice!!!!
1. Illustrate the open chain and cyclic
structures (both Haworth’s and chair) of
the following:
a. galactose
b. mannose
Trivia: α-D-mannose is a sweet-tasting sugar
while β-D-mannose tastes bitter…
II. Disaccharides- sugar formed when two
monosaccharide units are joined by glycosidic bond. They
can be hydrolyzed into simple sugars. MF: C12H22O11
A. Reducing disaccharides or reducing
sugars – has free anomeric carbon
1. maltose- α-D-glu + α-D-glu linked at α 1,4
2. cellobiose – β-D-glu + β-D-glu linked at β 1,4
3. lactose – β-D-gal + α or β-D-glu linked at β 1,4
4. melibiose – α-D-gal + α-D-glu linked at α 1,6
How are disaccharides formed?

• 2 glucose molecules are combined using a condensation reaction, with

the removal of water.
 Maltose
• Also known as malt
sugar; sugar in beer
• forms on the partial
hydrolysis of starch
 Cellobiose
• occurs naturally as
part of the cellulose.
• Humans can derive
cellobiose from foods
like honey, corn
syrups, certain fruits,
and vegetables.
• But humans do not
readily digest
cellobiose.
 LACTOSE
• Milk sugar
• Joined by β-1,4-
glycosidic bond
• occurs in the milk of
mammals
• 4-6% in cow's milk
• 5-8% in human milk.
• What is lactose
intolerance?
 Melibiose
• disaccharide consisting
of gal and glu in an
alpha (1-6) glycosidic
linkage.
• The sugar is produced
& metabolized only by
enteric & lactic acid
bacteria and other
microbes.
B. Non-Reducing Disaccharides of Non-
reducing sugars – has no free anomeric
carbon.
1. sucrose – α-D-glu + β-D fru linked at α,β 1,2
2. trehalose - α-D-glu + α-D-glu linked at α,α 1,1
 Sucrose
• Table sugar
• Obtained from sugar
cane or sugar beets
• Most abundant of all
disaccharides.
 Trehalose
• Major CHO energy
storage molecule used
by insects for flights.
• Mushroom sugar
• Makes shrimps sweet
• Is about 45% the
sweetness of sucrose
 Exercise 2
Answer the following:
Given: 1. Identify
Sugar A ____________
x Sugar B ____________
Sugar C ____________
A
Note: Complete name with
its anomeric form

2. Identify glycosidic bond

x_____________
B
y _____________

C 3. Which of the sugars are

y aldose/s________________
ketose/s _______________
 Exercise 3
Answer the following:
Given: 1. What is the anomeric form of
Sugar A= Sugar C =
A Sugar B = Sugar D =
x 2. Identify sugar
A = C=
B= D=
B 3. Identify glycosidic bond
y x= z=
y=
4. Which sugar is
C a. sweetest natural sugar=
z b. also known as brain sugar=
_________
D c. found in the blood =
 Reaction of Hexoses
• Hexoses like glucose, galactose and
mannose are physiologically important
sugars.
• These sugars are either reduced or oxidized,
and are fermented.
 Reaction of Hexoses
1-a. Reduction

CHO CH2OH
│ Pt │
(CHOH)4 + H2 (CHOH)4
│ │
CH2OH CH2OH

Hexose Hexitol (sugar alcohol)

Glucose sorbitol
Galactose galactitol
Mannose mannitol
 Reaction of Hexoses
1-b. Reduction

CHO CH2OH
│ E │
(CHOH)4 (CHOH)4
│ │
CH2OH CH2OH

Hexose Hexitol (sugar alcohol)

E = glucose reductase
Glucose sorbitol
Galactose galactitol
Mannose mannitol
 Reaction of Hexoses
2. Mild Oxidation
➢Mild oxidizing agents: Fehling’s, Tollen’s and
Benedict’s reagent
CHO COOH
│ (o) │
(CHOH)4 + Cu+2 (CHOH)4 + Cu+1
│ │
CH2OH CH2OH

Hexose Hexonic acid

Glucose gluconic acid

Galactose galactonic acid
mannonic acid
 Reaction of Hexoses
3. Moderate Oxidation in the living cell

CHO CHO
│ (o) │
(CHOH)4 + (CHOH)4
│ E │
CH2OH COOH

Hexose Hexuronic acid

Glucose glucuronic acid

Galactose galacturonic acid
Mannose mannuronic acid
 Reaction of Hexoses
4. Strong oxidation – conc. HNO3

CHO COOH
│ (o) │
(CHOH)4 + HNO3 (CHOH)4
│ │
CH2OH COOH

Hexose Hexaric acid

Glucose glucaric acid

Galactose galactaric acid or mucic acid
Mannose mannaric acid
 Reaction of Hexoses
5. Fermentation = yeast : invertase, zymase
Sucrose = glu + fru + zymase

C6H12O6 2CO2 + C2H5OH

 Reaction of Hexoses
6. Combustion

C6H12O6 + 6O2 6CO2 + 6H2O + 4 kcal/g

180g/mole
 Reaction of Hexoses
7. Phosphorylation

E = glucose hexokinase
 Assignment 1
1. Show the glycosidic bond formation of the following
disaccharides using chair conformation:
a. lactose B. melibiose C. trehalose
2. Given:

Answer the following:

a. Classification of the given.
b. Label anomeric carbons by circling them.
c. Draw an arrow pointing to the glycosidic bond. Is the glycosidic bond
connected to both anomeric carbons?
d. Classify the glycosidic bonds using the alpha or beta format
e. If the glycosidic bond is hydrolyzed, what are the names of the
monosaccharides produced, include whether its alpha or beta
III. Oligosaccharides - yield three to ten
monosaccharide units on hydrolysis.

A. Trisaccharides – MF: C18H32O21

Example: Raffinose – D-gal + D-glu + D-fru
glycosidic bonds at: gal(α-1→6) –glu-( α– 1→ β-2)fru

B. Tetrasaccharide- MF: C24H42O2

Example: Stachyose- D-Gal+D-gal +D-Glu+ D-fru
gal(α-1→6)gal(α-1→6)glc(α-1↔2-β)fru
 Raffinose
• It is present in sugar beet, cotton seed,
beans, cabbage, brussels sprouts,
broccoli, asparagus, other vegetables, and
whole grains.
 Stachyose
Stachyose - occurs naturally in numerous vegetables like green beans, soy
beans, and other beans and other plants.
- is less sweet than sucrose, at about 28% on a weight basis.
- is not completely digestible by humans and delivers 1.5 to
2.4 kcal/g thus causes flatulence.
 Relative Sweetness of Sugar
• Natural sugars
Fru – 173 lac - 16
Glu – 74 suc – 100 (reference)
Gal -32
• Artificial sweeteners Sugar alcohols
aspartame – 180 sorbitol - 60
saccharin – 300 mannitol – 50
sucralose – 600
neotame - 7000
 Interesting Facts about Sugar
• Sugar is 100% natural with no fat.
• Sure' and 'Sugar' are the only two words in
the English language that are spelt 'su' and
pronounced 'sh‘
• A can of Coke has 39 grams of sugar and a
can of Pepsi has 41 grams of sugar. That is
about seven teaspoons or 13 lumps of sugar
per can!
 Interesting Facts about Sugar
• A grain of sugar under the microscope is a
translucent crystal, reflecting light from its
14 facets like a jewel
• One Candy Bar has the same amount of
sugar as 10 apples.
• Sugar hardens asphalt. It slows the setting
of ready-mixed concrete and glue.
• Sugar feeds cancer cells.
Lesson 2 - Polysaccharides
Learning Objectives:
At the end of the lesson, the learners will be able to:
• Discuss the general characteristics of
polysaccharides.
• Compare storage polysaccharides from
structural polysaccharides based on source,
structure and function.
• Identify sugar components of polysaccharides.
• Discuss dietary considerations and
carbohydrates.
 Polysaccharides
• are polymeric carbohydrate structures of
simple sugars (monosaccharides) linked
together by glycosidic bonds.
https://www.sciencedirect.com/topics/food-science/polysaccharides

• All of the common polysaccharides contain

glucose as the monosaccharide unit.
• Polysaccharides are synthesized by plants,
animals, and humans to be stored for food,
structural support, or metabolized for energy.
 Classification of Polysaccharides
A. Energy storage polysaccharides
1. starch
2. glycogen
3. inulin
4. dextran
B. Structural polysaccharides
1. cellulose
2. pectin
3. alginic acid
4. agar
5. chitin
 Energy Storage Polysaccharides
1. STARCH
• Is a glucosan which yields only α-D-glucose on
hydrolysis.
• Most important source of CHOs.
• Found in cereals, potatoes, legumes, and
other vegetables.
• Natural starch is insoluble in water.
 Chief components of starch
a. Amylose
• Non-branched, helical structure, soluble part.
• Gives deep blue color with iodine.
• Accounts for about 20% by weight of starch
and consists of several hundred of glucose
molecules linked together by α 1,4-glycosidic
bonds.
• Its molecular weight ranges from 70,000-
500,000 g/mole.
 Chief components of starch
b. Amylopectin
• Accounts for the remaining 80% of the insoluble
part of starch and is more complex in structure
than amylose.
• Consists of highly branched chains.
• Gives red-violet color with iodine.
• Glucose molecules are linked by α-1,4 at the
linear portion and α-1,6 glycosidic bonds for the
branched portion. Its consists of up to 24-30
glucose residues.
• Stages Hydrolysis of starch
• Starch can be hydrolyzed with the use of an acid
(HCl) or enzyme (amylase).

• Starch → amylodextrin → erythrodextrin →

achrodextrin → maltose → α-D-glucose

 Energy Storage Polysaccharides
2. GLYCOGEN
• Reserved carbohydrates in animals
• More highly branched than amylopectin
• Is non-reducing
• Gives a mahogany red color with I2
 Energy Storage Polysaccharides
3. INULIN
• Starch found in tubers and roots of many plants.
• A fructosan, yields fructose on hydrolysis.
• Gives no color with iodine.
• It has been used in physiologic investigation for
determination of the rate of glomerular function.
https://pubchem.ncbi.nlm.nih.gov/compound/Inulin
 Energy Storage Polysaccharides
4. DEXTRAN
• a group of bacterial polyglucan composed of
chains of D - glucose units connected by α - (1-6)
glycosidic bond.
• are synthesized by a number of bacterial species.
• is commercially available & used as drugs,
especially as blood plasma volume expander.
• In food industry, it is currently used as thickener
for jam and ice-cream.
• It prevents crystallization of sugar, improves
moisture retention and maintains flavor and
appearance of various food items
• https://www.researchgate.net/publication/287480306_Dextran
 Structural Polysaccharides
1. CELLULOSE
• Nature uses cellulose primarily as a structural
material to impart strength and rigidity to
plants.
• Leaves, grasses and cotton are primarily cellulose.
• Made up of straight chains of ß-D-glucose units
linked by ß-1,4-glycosidic bond.
• Gives no color w/ iodine.
Cellulose

Note: 4 H-bonds are formed between 2 molecules of

cellulose as pointed by an arrow above.
The ability of these chains to hydrogen-bond together
forms into fibers that will give cellulose its unique
properties of mechanical strength and chemical stability.
 Cellulose – FIBER IN THE DIET
• Dietary fibers are food components not assimilated by
humans because of the absence of enzyme cellulase.
• These dietary fibers are responsible for enlargement of
fecal size, thus aiding in prevention of constipation.
Aside from this, consumption of fiber diets is found to
lower the risks of acquiring colon cancer.
• Dietary fibers may control also cholesterol absorption
through binding of the bile acids. High fiber diet could
decrease serum cholesterol productions, thus
preventing cardiovascular disease.
• These beneficial dietary fibers are often found in
various fruits, vegetables, nuts, and grains.
 Structural Polysaccharides
2. PECTIN
• Is a gelatinizing substance which is abundant in fruit
juices.
• Has a remarkable jelly-forming capacity, thus used in
food industry.
 Structural Polysaccharides
3. ALGINIC ACID
• Is the structural polysaccharide in the cell walls of brown
algae.
• A hydrophilic linear-like cellulose which forms a viscous gum
when hydrated.
• Used as thickener, emulsifier, and stabilizer and as a
hydrophilic agent in medical and cosmetic ointment bases.
Trivia: Gaviscon ,an
antacid contains alginic acid which is
made from seaweeds. Alginic
acid makes a protective foam layer that
floats on top of the contents of our
stomach. This stops stomach acid
escaping into our food pipe.
 Structural Polysaccharides
4. AGAR
• Structural polysaccharide which occurs in red algae, a
polymer made up of galactose subunits.
• Used as a microbial medium.
• Used as a component of a number of cosmetic and
pharmaceutical preparations.
 Structural Polysaccharides
5. CHITIN
• Structural polysaccharide made from chains of
modified glucose found in the shells of crustaceans
& insects, exoskeleton of arthropods and the cell
walls of fungi.
 Dietary Considerations and CHO
Contrast the dietary carbohydrate classifications simple carbohydrate and complex
carbohydrate;
Contrast the term natural sugar and refined sugar.
Current nutritional recommendation: a balanced diet should ideally be about 60% CHO
Nutritionists subdivide dietary CHOs into two categories:
a) Simple CHO – is a dietary monosaccharide or dietary disaccharide. Simple
carbohydrates are usually sweet to the taste and are commonly referred to as sugars.
natural sugar- sugar naturally present in whole foods. Milk and fresh
fruit are two important sources of natural sugars.
refined sugar- is a sugar that has been separated from its plant
source. Sugar beets and sugar cane are major sources of
refined sugar.
1 tsp refined table sugar = 50 cal. Of energy alone, no other nutrients
1 small orange = 50 cal of energy ,Vit C, K, Ca, fiber
b) Complex CHO – is a dietary polysaccharide. The main complex CHOs are starch and
cellulose, generally not sweet to the taste. Grains are the important source of both starch
and fiber as well as protein, vitamins and minerals. The pulp of a potato provides starch,
and the skin provides fiber. Broccoli and green beans are low in starch but high in fiber.
 Glycolipids and Glycoproteins
Glycolipids and Glycoproteins - are molecules in which oligosaccharides are attached
through glycosidic linkages to lipids and proteins respectively. Such molecules often govern
how cells of differing function interact with each other.

Glycolipids – is a lipid molecule that has one or more carbohydrate ( or CHO derivative)
units covalently bonded to it.
- called cerebrosides and gangliosides occur extensively in brain tissue.
Glycoproteins – is a protein molecule that has one or more CHO ( or CHO derivative) units
covalently bonded to it.
- called immunoglobins are key components of the body’s immune system
response to invading foreign materials.
Research work: 1. Hyaluronic acid
2. Heparin
Format:
1. Short introduction
2. Functions/uses
3. Focus on its molecular structure by identifying
the components that make up hyaluronic acid;
heparin
4. Discuss its properties
5. Trivia
Thank You!