Unit 3

Carbohydrates and glycobiology

1. Monosaccharides, disaccharides and
polysaccharides

2. Proteoglycans, peptidoglycans and glycoproteins:

Glycobiology, the language of sugars
 Carbohydrates

1. They are the most abundant biomolecules

2. Composed of hydrated carbon chains (CH2O)n

3. Carbon atoms bound:

Hydrogen atoms (H)
Hydroxyl groups (OH)
Carbonyl groups  - aldehyde or -ketone

Hydroxyl (Alcohol)
R – O–H

Carbonyl (Aldehyde) Carbonyl (Ketone)

R–C–H R1 – C – R2
O O
 Carbohydrates properties and functions

Sweet taste, dehydrated crystals soluble in water.

1. Main source of energy
2. Structural components
3. Participate in protein and cell recognition
 Monosaccharides

• Classification:
• Regarding their functional  Regarding C number:
group:
▪ 3 – Trioses.
• Aldoses –Aldehyde group.
• Ketoses – Ketone group. ▪ 4 – Tetroses.
▪ 5 – Pentoses.
▪ 6 – Hexoses.
▪ 7 – Heptoses.

Aldotrioses, Ketotrioses, …
 Monosaccharides

Fischer linear projection

 Paper plane.
 Carbonated chain in vertical.
Three Carbons
 More oxidized functional H O
group at the top of the C CH2OH
projection
H C OH C O
 The residues in horizontal
planes CH2OH CH2OH
Asimetric
D-Glyceraldehyde Dihydroxiacetone
carbon

OPTICAL Isomerism -> The configuration of the –OH that is farthest from the aldehyde function
(carbon 5) is in all D isomers equal to that of D-glyceraldehyde.
 Monosaccharides of Interest
in Human Biochemistry

Aldohexoses

H O H O H O
C C C
H C OH HO C H H C OH
HO C H HO C H HO C H
H C OH H C OH HO C H
H C OH H C OH H C OH
CH2OH CH2OH CH2OH

D-Glucose D-Mannose D-Galactose

Mannose and Galactose are Glucose (Glc)

diastereoisomers
All are convertible in Glc!
 Monosaccharides of Interest
in Human Biochemistry

Aldopentose A glucose derivate that forms part of

the nucleic acids

H O
C Cetohexose
H C OH
H C OH CH2OH
H C OH C O
CH2OH HO C H
H C OH
D-Ribose H C OH
CH2OH
- Both of them are
D-Fructose convertible in Glc
 Glucose
Is the blood sugar
Is the monosaccharide used by cells from different organs as fuel
(source of energy)
● Brain
If there is not enough Glc in the blood:
● Erythrocytes HYPOGLYCEMIA: confusion, disorientation

● Muscle Glc is transformed into energy for exercise

The level of Glc needs to be maintained in the blood

The Glc of the diet is kept in the blood for 2-3h

thereafter, Glc can be obtained from Glycogen

It is synthetized though Glycogenogenesis

Glycogen is a glc polysaccharide after meals
that acts as reserve of energy
It decomposes into Glc 3h after meals: Gradual
glycogenolysis up to 12h.
 Glucose

Diabetes The patient does not regulate the level of Glc in the blood
Diabetic symptoms

There is still
Weight not a perfect
device able to
Polyuria Polydipsia loss control glc
levels in these
patients!

Lack of Mood
Polyphagia energy swings Blurred vision
 Monosaccharides Cyclic structure

Monosaccharides in the blood (in aqueous solution) are found in cyclic form

β-

β- isomer

α- isomer

Carbon number 1 becomes asymmetric

It is the Anomeric carbon – a highly reactive
carbon with strong reduction power
 Disaccharides

Disaccharides are formed by the binding of two monosaccharides through

a O-glycosidic linkage. This reaction produces a water molecule

H 2O

α-D-Glucose β-D-Glucose Maltose

α-D-glucopiranosil-(1→4)-D-glucopiranose

● The new bond is formed between

the -OH of anomeric C (the most
reactive one) and any –OH
● The O acts as a bridge in the
linkage
 Disaccharides

• Maltose (polisaccharide)  Saccharose (sugar):

Glc α1→4 Glc Glc α1→β2 Fru

• Lactose (Milk): O
Gal β1→4 Glc

Saccharose loses its reduction

power since fructose loose its
anomeric carbon!
 Polysaccharides or Glycans: Nutrient reserve

Consist of many monosaccharide units joined by glycosidic bonds.

They can be classify according on their Anomer α -> nutrient reserve

function, and their function is defined by Glycogen and Starch
the anomer driving the glycosidic linkage Anomer β -> structural function
Cellulose

Glycogen – It is the Glc store in animals: stored energy for the organism.

10% liver mass (granules) and 1-2% muscle mass.

 Polysaccharides or Glycans
Glycogen structure - Amylopectin
Glc molecules are linked by α-glycosidic bonds (C1→C4) forming long chains. At certain points,
the chain branches out by an α-glycosidic linkage from carbon 1 of the first glucose of the
chain, to carbon 6 of a glucose molecule in other chain (α-1→6). The branches are separated
from each other by a distance of 8–12 glucose molecules

Non reducing
end of the
chain

Reducing end
of the chain
 Polysaccharides or Glycans: Nutrient reserve

Glycogen structure - Amylopectin

• Micellar-like structure, poorly
soluble in water.
• The non-reducing, degradation ends
on the outside of the micelle:
facilitates the obtaining of Glc.
• If this amount of Glc were free in
the cell, water would enter and
osmolarity would increase a lot
 Polysaccharides or Glycans: Nutrient reserve

Starch is the main carbohydrate in the human diet. It is found abundantly in cereals,
potatoes, and some vegetables
Starch structure – Amylopectin (80%) and Amylose (20%)

Amylopeptin - Similar to glycogen amylopeptin but branches α(1 → 6) are separated from each
other by a distance of 24–30 glucose residues

Amylose – Glucose form linera long chains in (α-1→4) bonds

It forms micellar-like structure, poorly soluble in water.
 Polysaccharides or Glycans: Nutrient reserve

Amylose α-1→4 bonds in a linear chain allows the chain to form a 3D helical structure
that coils around a central axis with six glucose molecules being contained
within each turn of the helix

The –OH groups of the monosaccharide residues are arranged on the outer
surface of the helix leaving the inside relatively hydrophobic.

In aqueous suspensions amylase molecules tend to associate and precipitate

 Polysaccharides or Glycans: Structural glycans

1. Cellulose is the most abundant organic compound in nature. It is a glucan that plays a
structural role in plants and is one of the main components of plant cell walls

2. Peptidoglycan form the bacteria cell wall that protects bacteria from changes in the
environment

3. Glycosaminoglycans or are linear polymers, formed by a succession of a

mucopolysaccharides disaccharide,form part of the extracellular matrix in animals

1. Cellulose

1. Main component of dietary fiber

2. Fibrous structure: insoluble in water.

3. Indigestible Glc polymer

4. O-glycosidic linkage Glc β1→4 glc

 Polysaccharides or Glycans: Structural glycans

Why is it fibrous?

1. Polysaccharide chains form layers joined

together by hidrogen-bonds

2. There are no –OH left

free to interact with
water.

3. They are stacked in fibers.

 Structural glycans – Cellulose VS Glycogen

Glycogen: helical structure, poorly soluble but

degradable.

Cellulose: fibrous structure, insoluble in water.

 Polysaccharides or Glycans: Structural glycans

2. Peptidoglycan

Bacteria cell wall is formed by strands of a polysaccharide whose structural units are N-acetyl-d-
glucosamine and N-acetylmuramic Acid. The strands run parallel to each other and are
interconnected by oligopeptides, which form a dense network that surrounds the entire bacteria.

Penicillin – Antibiotic to treat bacterial infections,

inhibits the synthesis of the cell wall
 Polysaccharides or Glycans: Structural glycans

3. Glycosaminoglycans

Linear polymers, formed by a succession of a disaccharide, generally composed

of an acidic sugar and an amine sugar.

(acidic sugar – amino sugar)n

O- They behave as polyanions thanks to

C-O- the existence of many ionizable groups
O=S=O CH2OH Carboxi groups (─COO−) and sulfate
O (─SO−3) in the molecule. They are found
in the extracellularmatrix (ECM) where
they trap water.
Glucuronic acid NH
C=O The ECM gets a gel-like
CH3 consistence
N-Acetil-Galactosamine
with one or more sulfuric groups
 Recognition and signalling glycans (glycobiology)

1. Proteoglycans - Glycosaminoglycans (GAG) + peptides or small proteins

2. Glycoproteins – proteins with sugars

3. Gycolipids – lipids with sugars

1. Proteoglycans

GAGs associated with proteins through

glycosidic linkages between the
polysaccharide chains and the hydroxyl
of serine or threonine, or the nitrogen
of asparagine residues in the protein.

The language
of sugars
 Recognition and signalling glycans (glycobiology)

2. Glycoproteins – conjugated proteins with carbohydrates as their non-aac component.

Glycoproteins differ from proteoglycans because their carbohydrate
chains are shorter (oligosaccharides) and branched.
Upon hydrolysis, they release more than two different types of monosaccharides.
The number of oligosaccharide chains in
glycoproteins is highly variable; from 1 (ovalbumin) to 800
Disaccharides in GAG
(proteoglycans) chains (submandibular gland glycoprotein).
Oligosaccharides increase diversity between proteins

Plasma membrane proteins

are, in general, highly
Oligosaccharides in glycosylated (OUTSIDE THE
glycoproteins CELL)

These cell-surface sugars are crucial for

regulating cell-cell contact and cell-
ECM interactions
 Recognition and signalling glycans (glycobiology)

3. Glycolipids are carbohydrate-containing lipids

The surface of red blood cells contain glycolipids

that act as antigens. The antigenic determinant
of these molecules lies in the carbohydrate
portion of the glycolipid

Depending on the oligosaccharide composition,

it is possible to characterize different groups of
individuals in a population. Several of these antigens
are known in humans; the best studied is
called AB0, which allows for the classification of
individuals into four groups (A, B, AB, and 0).
 Recognition and signalling glycans (glycobiology)

The complexity and diversity of carbohydrates in glycoproteins makes them suitable molecules
to contain information. The oligosaccharides on the cell surface represent “markers” or
“signals” that serve for recognition.

A glycoprotein of the ovule, zona pellucida 3

(ZP3) contains oligosaccharides recognized by
receptors on the surface of sperm. This allows
the interaction of female and male gametes prior
to fertilization.

Carbohydrates in glycoproteins and glycolipids drive

the adhesion of bacteria, viruses, and toxins Previous incubation of bacteria with
to the cell surface of cell membranes. the carbohydrate that they selectively
recognize, loose their invasive ability

Changes in surface oligosaccharides have been observed in

malignant tumor cells. The alteration of the signals that
determine the “social relations” among cells contribute to
the uncontrolled cell growth and multiplication