Chemistry of

Carbohydrates
by

R. Mautsa
L2
 Expected Outcomes
• Give uses of carbohydrates in living
organisms

• Identify functional groups in carbohydrates

• Relate structure of different carbohydrates

to their function
 Carbohydrates - Overview
• All carbohydrates are formed from the simple
sugars called monosaccharide.

• Major source of energy from our diet

• Also called saccharides, which means “sugars”

• Composed of elements carbon, C, hydrogen, H &

oxygen, O
– General formula is (CH2O)n or Cn(H2O)n
 Carbohydrates - Overview
• Carbohydrate = polyhydroxy aldehyde,
polyhydroxy ketone, or a compound that gives
either of these compounds after hydrolysis

Structures of a polyhydroxy aldehyde (left) and polyhydroxy ketone (right).

 Carbohydrates - Overview
• Are produced by
photosynthesis in plants
– Eg glucose is synthesized in
plants from CO2, H2O & energy
from sun

• Are oxidized in living cells

to produce CO2, H2O &
energy
 Carbohydrates - Examples
• Sugars, eg. in honey, table sugar

• Starch, eg. in rice, bread

• Cellulose, eg in fruits & vegetables

• Glycogen, eg stored in muscles & liver

 Carbohydrates - Functions
• Yield energy (ATP) to drive metabolic processes

• Energy-storage molecules, i.e., glycogen, starch

• Structural molecules - cell walls & exoskeletons of

some organisms

• Carbohydrate derivatives found in coenzymes, e.g.,

FAD & in nucleotides
 Types of Carbohydrates

1. Monosaccharides - (CH2O)n where n = 3-7

– one sugar molecule/residue
– simplest carbohydrates

2. Oligosaccharides - 2-10 sugar residues

 Types of Carbohydrates

3. Polysaccharides - polymers of > 10

sugar residues

4. Glycoconjugates – derivatives
– attached to proteins or lipids
 1. Monosaccharides
• Monosaccharides are simple sugars.

• They cannot be hydrolyzed into a simpler

form.

• The simplest carbohydrates are the 3-carbon

dihydroxyacetone and trioses glyceraldehyde.

• They are further classified into glucose,

fructose, galactose, and mannose
simple sugars might be further
divided into tetroses, trioses,
hexoses or heptoses, pentoses
and as ketoses or aldoses
based on whether the ketone or
aldehyde groups are present.
 Monosaccharides
Consist of:
• 3-7 carbon atoms typically
– divided into trioses, tetroses, pentoses
hexoses, or heptoses
• a carbonyl group
– divided as ketoses or aldoses based on
whether the ketone or aldehyde groups are
present
• several hydroxyl groups
 Monosaccharides
• Aldoses & Ketoses
• 2 types of monosaccharide structures:
– aldoses &
– ketoses
– polyhydroxy aldehydes or ketones
– Classified based on the type of carbonyl group & no. of
C atoms
CHO CH2 OH
CHOH C= O
CH2 OH CH2 OH
Glyceraldehyde D ihydroxyacetone
(an aldotriose) (a ketotriose)
 Monosaccharides: Aldoses
O
Aldoses are ║
monosaccharides: C─H
• with an aldehyde group │
• with many hydroxyl (-OH) H ─ C─OH
groups. │
triose (3C atoms) H─ C─OH
tetrose (4C atoms) │
pentose (5 C atoms) CH2OH
hexose (6 C atoms)
Erythose, an aldotetrose
 Monosaccharides: Ketoses
Ketoses are CH2OH
monosaccharides: │
• with a ketone group C=O
• with many hydroxyl │
(OH) groups H─ C─OH
│
• Eg. Fructose, a H─ C─OH
ketohexose │
H─C─OH
│
CH2OH
Monosaccharides: Aldoses and
ketoses
 Physical Properties of
Monosaccharides
• Colorless crystalline solids
• Sweet taste
• Very soluble in water
• But only slightly soluble in ethanol
• Their solutions are optically active and
exhibit mutarotation.
- Carbohydrates spontaneously change between the α and
β configuration.
 Structures of
Monosaccharides

• Fischer Projections
– D & L Notations
• Cyclic Structures
 Fischer Projections
A Fischer projection:
• 2-dimensional representation for showing
the configuration of carbohydrates
 Fischer Projections
A Fischer projection used to represent
carbohydrates:

• Places the most oxidized group at the top

• Shows chiral carbons as the intersection of vertical
and horizontal lines
• Shows the –H and –OH groups on the intersecting
line
• Places the – CH2OH group at the bottom of the
Fischer projection, which is not chiral
 Fischer Projections:
D & L Notations
• All sugars larger than trioses have two or more chiral groups,
and so exist as several stereoisomers.

• In a Fischer projection, OH group on chiral carbon farthest

from the carbonyl group determines an L or D isomer
– stereoisomers

• left is assigned letter L for L-form

• right is assigned letter D for D-form

– Predominates
– Virtually all sugars found in biological systems are D-isomers.
D & L Notations
 D & L Notations
• D-glucose D-ribose L-galactose
O
O
C H
C H
O
HO H
H OH
C H
H OH
HO H H OH
H OH
H OH H OH
H OH HO H
H OH
C H2O H C H2O H
C H2O H

Chiral atom farthest from the carbonyl group

 D-Glucose

• found in fruits, corn syrup, & honey

• aldohexose with formula C6H12O6

• known as blood sugar

• monosaccharide in polymers of starch,

cellulose, & glycogen
 Different forms of glucose
• D-Glucose, also known as dextrose, is found in all
cells and in blood plasma, where its concentration is
strictly controlled.

• Glucose is a six-carbon sugar, or hexose, formula,

C6H12O6.

• It can exist in four different forms, all of which are

freely convertible in aqueous solution (straight chain
form and cyclic forms)
 Different forms of glucose
• The straight chain form (which exists as less than 1%)
has an aldehyde group at one end (where the carbon is
always called carbon-1).
 Different forms of glucose
A reaction between the hydroxyl group on C5 and the
aldehyde on C1 on a straight chain glucose produces
a six-member ring form called a pyranose ring.
Formation of Cyclic Glucose
 Different forms of glucose
• Depending on the
arrangement of the -H and
-OH on carbon-1, the
glucose molecule forms
either -  or  -glucose
(also known as  -D-
glucopyranose and  -D
glucopyranose).

• These different forms are

known as anomers.
 Alpha and beta Glucose
Alpha glucose Beta glucose

In beta glucose the OH is

above the ring structure
 Different forms of glucose
• While the cyclic form of D-glucose is usually a
pyranose ring, rarely it can also form a five-
member furanose ring, D-glucofuranose.
• It is formed if the hydroxyl group is on C4 then
 Chair and boat conformations
• Due to the tetrahedral arrangement of bonds around
the carbon atoms, the pyranose and furanose rings
are not planar molecules.

• They form two different arrangements, known as the

chair and boat conformations.

• These conformations are important for the packing of

the molecules, although the chair conformation is the
more stable.
 Chair and boat conformations
• Orientations of groups on carbons 1-5 in Haworth
& chair projections of -D-glucopyranose are up-
down-up-down-up

6 CH OH
2 6
5 O CH2 OH
H OH() 4
H HO O
4 OH 1 HO 5
H
HO H 2 OH( )
3 3
2 OH 1
H OH
-D -Glucopyranose -D -Glu copyran os e
(Haw orth projection) (chair conformation )
 Mutarotation

• Mutarotation = change in specific rotation that

occurs when an  or  form of a carbohydrate is
converted to an equilibrium mixture of the two
 -D-Glucose & β-D-Glucose
in Solution
When placed in solution,
• cyclic structures open & close
• -D-glucose converts to β-D-glucose & vice versa
• at any time, only a small amount of open chain forms
CH2OH CH2 OH CH2OH
H
O O O
OH
O
OH C
OH OH
H OH
OH OH OH

OH OH OH
-D-glucose D-glucose (open) β-D-glucose
(36%) (trace) (64%)
-D-Glucose & β-D-Glucose
in Solution
 Derivatives of Monosaccharides
• Deoxy sugars
• Glycosides
• Sugar Phosphates
• Amino sugars
• Sugar alcohols
• Sugar acids
Derivatives of Monosaccharides
Deoxy sugars
• H atom replaces -OH group on C-2
• Important to structure of nucleic acids
Derivatives of Monosaccharides
Glycosides
• Sugar in which the -OH of the anomeric
carbon is replaced by -OR.
– Eg. methyl -D-glucopyranoside = methyl -D-
glucoside
glycos idic
bond
CH2 OH CH2 OH CH2 OH
O OH O OCH3 OH
H + H H
H H H H
OH H + CH3 OH OH H + OH H
HO -H2 O H HO OCH3
H HO
H OH H OH H OH
-D -Glu copyran os e Methyl -D -glu co- Meth yl -D -glu co-
(-D -Glu cose) pyran os ide p yranosid e
( Methyl -D -glucos ide) (Methyl -D -glucos ide)
Derivatives of Monosaccharides
Glycosides
• Anomeric C-atom of a cyclic hemiacetal also
undergoes reaction with N-H group of an amine to
form an N-glycoside
• The -N-glycoside formed between D-ribofuranose
and cytosine
NH2

N a -N -glycosid ic
bond
O N
HOCH2 O
H H
H H anomeric
HO OH carbon
 Pentoses
• Pentose monosaccharides contain 5-C atoms
• The structural isomers ribose & deoxyribose are
important constituents of RNA & DNA
• Ribose has 1 H atom & one –OH group attached
to C-2, whereas deoxyribose has 2 H atoms and
no –OH group.
CHO CHO
CHO H OH H H
O H H OH H OH
H OH H OH H OH
CH2 OH CH2 OH CH2 OH
D-Threose D-Ribose 2-Deoxy-D-
ribose
Derivatives of Monosaccharides
Sugar phosphates
• Esterification between –OH group of sugar
and phosphoric acid
Derivatives of Monosaccharides
Sugar phosphates
Phosphate esters of monosaccharides are
found:
• In the sugar-phosphate backbone of DNA &
RNA
• In ATP
• As intermediates in the metabolism of
carbohydrates in the body
 Derivatives of Monosaccharides
Amino sugars
• Amino group (NH-) substitutes -OH group in
monosaccharide
CHO CHO CHO CHO O
H NH2 H2 N 2 H H NH2 H NHCCH3
HO H HO H HO H HO H
H OH H OH HO 4 H H OH
H OH H OH H OH H OH
CH2 OH CH2 OH CH2 OH CH2 OH
D-Glucosamine D-Mannosamine D-Galactosamine N-Acetyl-D-
glucosamine

2-amino-D-glucopyranose
 Derivatives of Monosaccharides
Sugar alcohols
• Produced by reduction of the C=O group in
an aldehyde or ketone
• Replace carbonyl O to form polyhydroxy
alcohols
– e.g. glyceraldehyde → glycerol
• Replace “-ose” with “-itol”.
– Ribose → ribitol
– Found in coenzyme FAD
 Derivatives of Monosaccharides
Sugar alcohols

CHO CH2 OH
CH2 OH H OH H OH
HO O HO H HO H
HO NaBH4
OH H OH H OH
OH H OH H OH
-D -Glucop yranose CH2 OH CH2 OH
D -Glu cose D -Glucitol
(D -Sorbitol)
 Derivatives of Monosaccharides
Sugar acids
• Oxidation of carbonyl C or highest C to carboxylic
acid
– ie aldehyde at C1, or OH at C6
– glucose → gluconate or glucuronate
– Important in many polysaccharides
 Derivatives of Monosaccharides
Sugar acids
CHO CHO
H OH enzyme-catalyzed H OH COOH
HO H oxidation HO H O
HO
H OH H OH HO OH
H OH H OH OH
CH2 OH COOH
D -Glucose D -Glucuronic acid
(a uronic acid)

Ascorbic acid
Derived from D-glucuronate
Primates cannot do the conversion,
→must be supplied in diet
 2. Oligosaccharides

• 2-10 sugar residues

Such as:
• disaccharides e.g., maltose
• Trisaccharide's e.g., raffinose
• tetra saccharides e.g., stachyose
 Example of Oligosaccharides:
Disaccharides
• The most abundant oligosaccharides
found in nature are the disaccharides
• 2 monosaccharides joined by covalent bond
– glycosidic linkage
– condensation reaction
• Bond is created between (OH) on C-1 of one
sugar & -OH of another sugar
 Disaccharides

A disaccharide consists of 2 monosaccharides

• Maltose, from barley = glucose + glucose + H2O
• Sucrose, table sugar = glucose + fructose + H2O
• Lactose, milk sugar = glucose + galactose+ H2O
 Maltose

• Also known as malt sugar

• Composed of 2 D-glucose molecules

• Obtained from hydrolysis of starch

• Used in cereals, sweets & brewing

• Found in both - & β - forms

Formation of Maltose

Free α-OH
 Lactose

• Disaccharide of β-D-galactose & α- or β-D-

glucose

• Contains a β -1,4-glycosidic bond

• Major carbohydrate found in milk & milk

products
Lactose
 Sucrose
• Table sugar
• Obtained from sugar cane & sugar beets
• Consists of α-D-glucose & β-D-fructose
• Has an α,β-1,2-glycosidic bond

α-D-glucose

β -D-fructose
 Reducing & Non-Reducing Sugars
• Some monosaccharides & most disaccharides
have a reactive carbonyl group or anomeric C
that can be oxidized
• Examples:
– glucose
– maltose
– lactose
 Reducing & Non-Reducing Sugars
• Detected by ability to reduce Cu2+ → Cu+ with
Benedict’s reagent
– blue → red-orange precipitate

• Non-reducing sugars have both anomeric C in a

glycosidic bond
– e.g. sucrose
 3. Polysaccharides
• Contains more than 10 sugar units

• Have high molecular weights and are sparingly

soluble in cold water

• Are also called glycans

• May be either linear or branched in structure

• Not sweet, and do not exhibit properties of

aldehyde or ketone groups
 Polysaccharides
Divided into 2 classes:
• homoglycans - homopolysaccharides
composed of 1 type of monosaccharide

• heteroglycans- heteropolysaccharides
made of more than 1 type of
monosaccharide
 Polysaccharides

Often classified according to their biological

role:
• starch & glycogen - storage
polysaccharides

• cellulose & chitin - structural

polysaccharides
 Starch & Glycogen

Both are homoglycans

• Starch is storage form in plants & fungi

• Glycogen is storage form in animals

• Bacteria contain both

 Starch
Mixture of amylose & amylopectin
• Amylose – continuous, unbranched polymer
of 100-1000 D-glucose
– linked by -(1→4) glycosidic bond

• Amylopectin - branched polymer

-(1→4) bond between glucose units
-(1→6) bond to branches
 Starch

• Overall, between 300-6000 glucose

residues

• With branches once every 25 residues

• Side chains 15-25 residues long

Structures of Amylose & Amylopectin
 Glycogen
• Polysaccharide that stores α-D-glucose in
muscle
• Branched polymer of glucose residues
– with branches every 8-12 residues
– containing up to 50 000 residues
• Similar to amylopectin, but is more highly
branched
 Cellulose
• Straight chain homoglycan of glucose with -
(1→4) linkages
• Every other glucose is flipped over, due to 
linkages.
• Extensive H-bonding within & between
cellulose chains
• Ranges in size from 300-15 000 glucose
residues
• Makes bundles or fibrils
– rigid
 Cellulose

• Cannot be digested by humans because

humans cannot break down β-1,4-glycosidic
bonds
 4. Glycoconjugates

Heteroglycans of 3 types:
• Proteoglycans
• Peptidoglycans
• Glycoproteins
 Proteoglycans
• The proteoglycans contain 95% carbohydrate.

• They are formed from two components: a linear polypeptide

chain attached to large, linear polysaccharide chains called
glycosaminoglycans (GAGs) or mucopolysaccharides

• Proteoglycans are glycosaminoglycans (GAGs) that are

covalently linked to serine residues of specific core proteins

• The glycosaminoglycan chain is synthesized by sequential

addition of sugar residues to the core protein

• Found in extracellular matrix of connective tissues, cartilage &

synovial fluid
 Proteoglycans
• Glycosaminoglycans are unbranched
heteroglycans of disaccharide units
– amino sugar, D-galactosamine or D-
glucosamine
– & alduronic acid
• e.g. hyaluronic acid
 Proteoglycans
• Acidic polysaccharides = mucopolysaccharides
present in connective tissue eg synovial fluid &
vitreous humor
CH 2OH
D-glucuronate 6
 H 5 O
6COO H
4 1 O
O H
H 5
H OH H
4 H 1 3 2
OH
H H NHCOCH 3
3 2 O
H OH N-acetyl-D-glucosamine
hyaluronate
 Function of
Glycosaminoglycans (GAGS)
• 1. They have the special ability to bind large amounts of water, there by
producing the gel-like matrix that forms the basis of the body’s ground
substance.
• 2. Since they are negatively charged, for example, in bone,
glycosaminoglycans attract and tightly bind cations like ca++, they also
take-up Na+ and K+
• 3. GAGs stabilize and support cellular and fibrous components of tissue
while helping maintain the water and salt balance of the body.
• 4. Its essential components of the extra cellular matrix, GAGs’ play an
important role in mediating cell-cell interactions
• • Ground substance is a part of connective tissue, which is a gel like
substance containing water, salt, proteins and polysaccharides.
• An example of specialized ground substance is the synovial fluid, which
serves as a lubricant in joints, and tendon sheaths.
 Peptidoglycans

• Found in cell wall of bacteria

• Composed of alternating residues of N-

acetylglucosamine & N-acetylmuramic
acid
– joined by (1→ 4) linkages
 Glycoproteins
• Proteins with oligosaccharides attached
• Carbohydrate chains,1-30 residues in length
• Examples:
– enzymes
– hormones
– structural proteins
– transport proteins
• Found in eukaryotic cells
 Glycoproteins
• Can be attached to proteins with one of 2
configurations:
– O-linked - carbohydrate bonded to -OH of serine
or threonine
– N-linked – carbohydrate, usually N-
acetylglucosamine, linked to asparagines
CH2OH O HN
CH2OH C O H O HN C CH2 CH Asn
H
O O CH2 CH H C O
H OH
H NH serine OH H HN
OH H residue HC R X
H HN C CH3
OH O H C O
O
H HN C CH3 N-acetylglucosamine HN

-D-N-acetylglucosamine Initial sugar in N-linked HC R Ser or Thr

glycoprotein oligosaccharide C O