Carbohydrates

ohydrates are aldehyde or ketone compounds with multi

xyl groups. They make up most of the organic matter on
because of their extensive roles in all forms of life
Chapter 11: Outline

Monosaccharides are aldehydes and ketones with multi

hydroxyl groups

Complex carbohydrates are formed by linkage of

monosaccharides

Carbohydrates can be attached to proteins to form

glycoproteins

Lectins are specific carbohydrate-binding proteins1

• Carbohydrates are aldehyde or
ketone compounds with multiple
hydroxyl groups.
• The basic molecular formula
(C.H2O)n where n = 3 or more.
• The term ―carbohydrate comes
from the observation that when you
heat sugars, you get carbon and
water (hence, hydrate of carbon).
- Carbohydrates are organic molecules found in nature,

constituting one of the four major classes of

biomolecules.

- The other three are proteins, nucleic acids and lipids.‐

- Saccharides (saccharo is Greek for ―sugar)-

 Properties of Carbohydrates

hydrates serve as energy stores, fuels, & metabolic

mediates

e & deoxyribose sugars form part of the structural

work of RNA & DNA

accharides are structural elements in the cell walls of

ria and plants. Cellulose is the most abundant organic
ound in the biosphere

hydrates are linked to many proteins and lipids, key role

diating interactions among cells - made possible by thei
structural diversity
4
 Classification
They are classified according to the number of structural units into:
1‐Monosaccharides= They are the simplest carbohydrates that can
not be hydrolysed into simpler units.
2‐ Disaccharides= produce 2 molecules of monosaccharide on
hydrolysis.
3‐ Oligosaccharides= produce three to ten monosaccharide units on
hydrolysis
4‐ Polysaccharides= : produce more than 10 monosaccharide units on
hydrolysis
 1- Monosaccarides

• * Def : They are the simplest

carbohydrate unites which can not be
hydrolyzed to a simpler form
• * General formula: (CH2O)n n≥3
 * Nomenclature:
• 1- According to active group in
the sugar:
– If monosaccharide contains
aldehyde group (CHO) → it's
called aldose.
– And if contain ketone group (c=o)
→ it's called ketose.
2‐ According to the number of carbon atoms
(n): If sugar contains
5c→ pentose
3 carbons → it's called triose, 4c→
6c→ hexose
tetrose 7c→
heptose
3- By combining the two methods , we find
3c-Aldotriose
that: -ketotriose
4c-Aldotetrose -ketotetrose
5c-Aldopentise -ketopentose
6c-Aldohexose -ketohexose

Three Carbon Four Carbon

Five Carbon
Six Carbon
 The structure of glucose can be represented in one of the
following ways:

1.The straight – chain (open ‐ chain) structural formula :

Aldohexose can account for some of the properties of glucose, but

can not explain some reaction

D-glucose
 Monosaccharides
Simplest carbohydrates, aldehydes or ketones with
two or more
hydroxyl groups
Empirical
Smallest formula, (C-H2O)n, literally
monosaccharides a “carbon
are trioses (n = 3)
hydrate”
Keto group Aldehyde group

Glyceraldehyde has 1 asymmetric C, thu

2 stereoisomers (D- & L-), are enantiome
12
mirror images of each other
 Dihydroxyacetone
No
asymmetric
carbon

Keto group

13
D-Glyceraldehyde

Aldehyde group

Asymmetric carbon

14
L-Glyceraldehyde

Aldehyde group

Asymmetric carbon

15
Fischer Projections

Stereochemical relations:

Horizontal bonds; in front of page plan

Vertical bonds; behind plane

16
 D-Aldoses (3,4,5, & 6 carbons)
Aldehyde group, blue Distal asymmetric cente
Numbering

17
 Triose & tetroses

Aldehyde group, blue

Distal asymmetric center

Note numbering

18
Tetrose & Pentoses

19
Tetrose & Pentoses

20
Pentoses & Hexoses

21
Pentoses & Hexoses

22
 D-Ketoses (3,4,5, & 6 carbons)
Keto group, blue
Numbering

Distal asymmetric cente

23
Triose & tetrose

24
Tetrose & Pentoses

25
Pentoses & Hexoses

26
A. Isomers and epimers
- Cpds that have same chemical formula but have
different structures = isomers e.g., fructose, glucose,
mannose, & galactose are all isomers of each other,
having same formula C6H12O6
- If 2 monosacch differ in configuration around only one
specific C atom (with exception of carbonyl C), they
are defined as epimers of each other (of course they
are also isomers) e.g.,
- glucose & galactose are C-4 epimers, their structures differ
only in the position of –OH group at C 4.
- Glucose & mannose are C-2 epimers
- however, galactose & mannose are not epimers, they differ in
position of –OH groups at two carbons, and defined only as
isomers
Note: carbons in sugars are numbered beginning at end
containing the carbonyl C i.e., aldehyde or keto group
Figure 7.4
C-2 and C-4 epimers and an isomer
of glucose.
B. Enantiomers
- A special type of isomerism is found in the pairs of
structures that are mirror images of each other. These
mirror images = enantiomers, & the 2 members of the
pair are designated as D- & L-sugar. Vast majority of
sugars in humans are D-sugars

Figure 7.5
Enantiomers (mirror
images) of glucose.
C. Cyclization of monosaccharides
- Less than 1% of each of the monosacch with 5 or
more C’s exist in the open-chain (acyclic) form. Rather,
they are predominantly found in ring form, in which
aldehyde (or ketone) group has reacted with an alcohol
group on the same sugar
1. Anomeric carbon:
- Formation of a ring results in creation of an anomeric
C at carbon 1 of an aldose or at carbon 2 of a ketose
- These structures are designated the α or β
configurations of the sugar, e.g., α-D-glucose & β-D-
glucose. They are both glucose, but are anomers of
each other
- Enz’s are able to distinguish b/w the 2 structures & use
one or the other preferentially e.g., glycogen is
synthesized from α-D-glucopyranose.
- The cyclic α & β anomers of a sugar in solution are in
equil. with each other, & can be spontaneously
interconverted (a process called mutarotation)
Figure 7.6. The interconversion of the α and β anomeric forms
of glucose (mutarotation).
Sugar ring formation
 Most sugar units of carbohydrates in nature (and thus
foods) have ring structures
 Formed by a reaction between the aldehyde or ketone
group and an –OH group of the sugar
 This results in ring structures called:
◦ Hemiacetal (aldoses)
◦ Hemiketal (ketoses)
 These can further react to create di-, oligo- and
polysaccharides (condensation reactions) and react with
alcohols

32
Formation of - and
-anomers of D-glucose

A new asymmetric center

is created and the carbon
at that center is known as
the anomeric carbon
(labeled *)
If the –OH is facing down
at C* then we have the -
anomer
If the –OH is facing up at
C* then we have the
-anomer

33
The most common sugar ring forms

 Pyranose
◦ Six-member rings
◦ More thermodynamically
favorable
◦ Most common
 Furanose
◦ Five-member rings
◦ More kinetically favorable

34
 Aldehydes cyclize (pentoses &
hexoses)
aldehyde can react with an alcohol to form a hemiaceta

35
 Ketones cyclize (pentoses & hexoses)
ketone can react with an alcohol to form a hemiketal

36
 5 & 6 membered rings
Furanose Pyranose

37
 Pyranose formation

Haworth projection

Fischer
projection Intramolecular
hemiacetal, 38
& L enantiomers at C52 anomers,  &  at C1
 Furanose formation (from hexose)

Haworth projection

Fischer
projection Intramolecular
hemiketal,
2 anomers,  &  at C2
39
& L enantiomers at C5
 Furanose formation (from pentoses)

C-1 is anomeric carbon,

-anomer, OH below ring plane
-anomer, OH above the plane
40
& L enantiomers at C4
Fructose ring structures

C5 to C2 bond

C6 to C2 bond

41
 -D-Fructofuranose

C5, D C2,

42
-D-Fructofuranose

C2, 

43
 -D-Fructopyranose

C5, D C2, 

44
 -D-Fructopyranose

C5, D C2, -anomer

45
Pyranose ring not planer

46
The more correct representation of the ring form
 The pyranose and Which is the more stable form?
furanose rings are not
flat
 For pyranose rings the
chair and boat forms are
better representations of
their actual structures
 The furanose rings are
present as either
envelope or twist
conformations

47
Chair & Boat forms

48
 Furanose ring not planer
Envelope form of -D-ribose

49
 Reducing sugars
lution of cupric ion, Cu2+ (Fehling’s solution),
st for reducing sugars such as glucose

Free aldehyde group is oxidized

50
2. Reducing sugars:
- If the oxygen on the anomeric C (the carbonyl
group) of a sugar is not attached to any other
structure, that sugar is a reducing sugar.
- A reducing sugar can react with chemical
reagents e.g., Benedict’s soln & reduce the
reactive component, with the anomeric C
becoming oxidized
Note: only the state of the oxygen on the anomeric
C determines if the sugar is reducing or non-
reducing, the other hydroxyl groups on the
molecule are not involved
 Glycosidic bonds
nosaccharides can react with alcohols & amines

glucose + methanol (acid-catalyzed), two products,  &

52
 Modified monosaccharides
equently expressed on cell surfaces

53
54
55
56
• Two monosaccharides can join with a glycosidic
linkage to form a dissaccharide via dehydration.
• Maltose, malt sugar, is formed by joining two glucose
molecules.
• Sucrose, table sugar, is formed by joining glucose and
fructose and is the major transport form of sugars in
plants.
• While often drawn as a linear skeleton, in aqueous
solutions monosaccharides form rings.
59
 Linkage of monosaccharides: Maltose, a
disaccharide
ucose molecules linked by an -1,4-glycosidic bond

C6

C6 C1

60
 Common disaccharides

Common
dietary
components

61
Disaccharides
 Classified
by many as the smallest oligosaccharides
 Formed by a condensation reaction between 2
monosaccharide units forming a glycosidic bond
 Most common:
◦ Sucrose
◦ Lactose
◦ Maltose

62
 Sucrose (table sugar from cane or
beet)

Hydrolyzed by sucrase
63
Sucrose (table sugar)
Note that Fructose
 has been flipped
Naturally present and that it is in the
 Popular ingredient in foods -position
(very large daily
consumption)
 Used widely in fermentation
 Different commercial forms
 Composed of glucose and
fructose -1-2
 The glycosidic bond is
formed between the anomeric
carbons of Glu and Fru
 This renders the anomeric The bond can be broken by hydrolysis
carbons non-reactive and the - Enzyme (fructosidase invertase)
sugar is therefore called a - Acid/heat
NON-REDUCING sugar Product called invert sugar

64
 Lactose (from milk)

Hydrolyzed by lactase in humans,

65
& by -galactosidase in bacteria
 Lactose
 Galactose and glucose
 The only sugar found in milk -1-4
◦ 4.8% in cows
◦ 6.7% in humans
◦ The primary carbohydrate source
for developing mammals
◦ Stimulates uptake and retention of
calcium
 Food products Reducing end

◦ Milk
◦ Unfermented dairy products Cleaved by lactase (enzyme)
◦ Fermented dairy products
 Contain less lactose
 Lactose converted to lactic acid

66
 Lactose
Problems with lactose in foods
A) Crystallization during drying
◦ Appearance of glass in milk powder
◦ Sandy texture in ice cream
◦ Sometimes dissolved while other times it will not dissolve
◦ -D-lactose VERY INSOLUBLE (5 gm/100 ml)
 Causes the glass-like appearance in foods
◦ -D-lactose MORE SOLUBLE (45 gm/100 ml)
◦ If >> more  will form
◦ Limits amounts of milk solids one can use in formulations
 Quick drying  get non-crystalline lactose (amorphous)  no crystalline
form
 Slow drying or concentration  more crystalline lactose

67
 Lactose
B) Color and flavor
◦ Lactose is a reducing sugar
◦ Can react with proteins and form undesirable color and
flavors
◦ Problem with dairy product and dairy ingredients,
especially during drying, concentration and heating
C) Lactose intolerance
◦ Some lack enzyme lactase
 Age and ethnic group related
◦ Lactase  lactic acid = problem for the intestines
 Gas, bloating, diarrhea, acid buildup
◦ Several ways to prevent or minimize this problem

68
 Maltose (from starch hydrolysis)

Hydrolyzed by maltase
69
 Maltose
 2 units of glucose
 Forms from the breakdown of starch during malting of grains (barley) and
commercially by using enzymes (-amylase)
◦ E.g. malt beverages; beer
 Used sparingly as mild sweetener in foods
 Very hygroscopic
 OH-group can be reactive and we term this as a REDUCING SUGAR
◦ Is free to react with oxidants

-1-4

Reducing end

70
 Tri- and tetrasaccharides
Galactosylsucroses
 Raffinose (3) and Stachyose (4)
◦ Found primarily in legumes Gal
◦ Poorly absorbed in small intestine Glu Fru
and indigestible
 We cant hydrolyze the  1-6 linkage
 Bacteria in intestines use it and
produce gas  Cause of flatulence Gal Glu
 “Flatulence is not socially acceptable
in some societies” really? Gal
◦ Possibly inhibited by phenolic Fru
compounds
◦ How do we minimize this problem?

71
Some properties of mono and oligosaccharides

RELATIVE SWEETNESS

SUGAR RELATIVE SWEETNESS SUGAR RELATIVE SWEETNESS

D-FRUCTOSE 175 RAFFINOSE 23

SUCROSE 100 STACHYOSE ---

-D-GLUCOSE 40-79 XYLITOL 90

-D-GLUCOSE <40 SORBITOL 63

-D-GALACTOSE 27 GALACTITOL 58

-D-GALACTOSE --- MALTITOL 68

-D-MANNOSE 59 LACTITOL 35

-D-MANNOSE BITTER
-D-LACTOSE 16-38
-D-LACTOSE 48
-D-MALTOSE 46-52 72
Chemical reactions
MUTAROTATION

Process by which various anomeric forms attain

an equilibrium in solution
First established studying spectral properties of
sugars
◦ Rotation of plane polarized light by an asymmetric
center
◦ Rotation varies from sugar to sugar and anomere

73
 Chemical reactions
MUTAROTATION

 = +112
 = +18.7

Equilibrium = +52.7

At equilibrium:
37% 
63% 

For any sugar - the occurrence of mutarotation

implies that a small amount of the straight
chain form must be present
74
 Chemical reactions
MUTAROTATION

~37%
<<1%

0.0026%
~63%

75
 EM of microvillus (in small intestine)
crase, lactase, & maltase, located on microvilli
oject from outer face of plasma membrane of
estinal epithelial cells)

76
 Polysaccharides: Glycogen (branch points)
lycogen is highly branched Glucose store

77
anch every 10 glucose units (approx)
 Glycosidic bonds determine structure

Straight chains,
Bent chains, good for structure
good for storage

78
 Cellulose
or structural polymer of plants,
of the most abundant organic compounds in the biosph

aight chain polymer of glucose,

ils formed by parallel chains, held by hydrogen bonds

mals lack cellulases, cannot digest wood or vegetable fi

ria hydrolyze it in the rumen
79
 Starch & glycogen (homopolymers)
pen helix, accessible stores of sugar,
arch in plants, glycogen in animals

Glycogen, highly branche

rch, two forms, (every 10 glucose units)
ylose - unbranched, 80
ylopectin - branched (every 30 glucose units)
D. Complex carbohydrates
- CHO’s can be attached by glycosidic bonds to non-
CHO structures e.g., purines & pyrimidines (found in
nucleic acids), aromatic rings (such as those found in
steroids & bilirubin), proteins (found in glycoproteins &
glycosaminoglycans), and lipids (found in glycolipids)
- The aldose (C1) or ketose (C2) participates in the
glycosidic link, is called glycosyl residue. E.g., if
anomeric C of glucose participates in such a bond,
that sugar = glucosyl residue; thus the disacch
lactose is galactosyl-glucose
1. O- & N-glycosides:
- If the group of the non-CHO molecule to which
sugar is attached is –OH group, the structure
is O-glycoside. If the group is –NH2, structure
is N-glycoside.
Note: all sugar-sugar glycosidic bonds are O-type
 Glycosaminoglycans, Anionic
Polysaccharides
of repeating disaccharide units, containing a derivative
o sugar, glucosamine or galactosamine
At least 1 of the sugars has a negatively charged
carboxyl or sulfate group

83
lly attached to proteins to form proteoglycan (95% carb
 Proteoglycan functions

• Lubricants for mucous membranes & connective tissue

• Structural components in connective tissue

• Mediate adhesion of cells to extracellular matrix

• Bind factors that stimulate cell proliferation

84
 Chondroitin 6-sufate

Found in cartilage 85
 Keratan sulfate

Found in hair, nails, etc 86

 Heparin

nticoagulant used to prevent blood clotting 87

 Dermatan sulfate

Found in skin 88
 Hyaluronate

und in connective tissue & serves as lubricant 89

Oligosaccharide synthesis:
Glycosyltransferases
Catalyze formation of
glycosidic bonds,

Each enzyme specific t

sugar,

Therefore, many
enzymes required

Unlike nucleic acid or

protein biosynthesis,
no template used

90
 Activated sugar nucleotide
mportant intermediates in many processes

91
Glycosidic bond formed

92
 A, B, & O oligosaccharide antigens (blood
groups)

Specific
glycosyltransferases
add group to O antigen

93
dation oligo(frameshift mutant gene), one from each par
Glycoproteins (small % of carbs), glycosidic
bonds
N-linked, Asn
in ER & Golgi

O-linked, Ser, Th
in Golgi only

Components of
cell membranes,
adhesion,
binding of sperm
to eggs

Some soluble
proteins also
94
N-linked oligos, high mannose type

95
N-linked oligos, complex

96
Elastase,secreted glycoprotein in
serum

Most proteins in
blood serum are
glycoproteins

97
ER & Golgi complex
Where proteins are
glycosylated following
synthesis on ribosome

N-linked in ER
O-linked in Golgi

Black dots on ER are

ribosomes

Electron
micrograph
98
 Transport into ER
lycosylation starts in ER lumen

99
Repeating unit of Dolichol Phosphate (in ER
membrane)

DP, specialized
lipid in ER
membrane - up to
20 isoprene

100
 Dolichol phosphate

ER membrane, phosphate group on cytoplasmic face

pid molecule on which oligosaccharides are assembled p

rotein glycosylation

101
 Assembly of N-linked oligos on Dol-P
Three stages

Cytoplasmic Flip ER lumem

102
Golgi complex, sorting center
Targets
proteins to,

Lysosomes,

Secretory
vesicles,

Plasma
membrane

103
Mannose 6-phosphate marker

Modification of mannos
residue in the oligo as
a marker for targeting t
Lysosomes

Done in cis Golgi

compartment

104
Step one

Phospho-N-acetylglucosamin

105
Step two

106
Quality control of protein folding in ER
Calnexin, &
(calreticulin)
chaparone
Proteins

Carbohydrates
carry
information

107
Oligo structure by mass spectrometry

108
 Plant lectins, binding selectivities

ree plant lectins bind different oligos

rve as insecticides

109
 Animal lectin, C-type carb-binding
domain
al cell lectins facilitate cell-cell contact
n binding sites on surface of one cell interacts with
s displayed on surface of another cell (like Velcro)

animal cell C-type lectins, Ca2+ ion acts as a bridge

ween protein and sugar residue of oligo 110
 Selectins, C-type lectins
mphocytes binding to lining of lymph nodes
Bind immune-
system cells
to targets,

L- to lymph-
node vessels,

E- to
endothelium,

P- to blood
platlets

111
Influenza hemagglutinin
Binds to sialic acid residue
on target cell surface,

Inside cell, viral protein,

neuraminidase, cleaves
glycosidic bond;
a promising target for
anti-influenza agents

112