Carbohydrate

Chemistry
Dr Genaro Wilfred Francisco C. Asis
Objectives

 1. Discuss the chemical diversity and significance of

carbohydrates
 2. Identify the chemical structure of the carbohydrate forms
and the various chemical reactions they can undergo
 3. Differentiate oligosaccharides
 4. Discuss various polysaccharides that exist in nature
Introduction

 “Carbohydrates” - hydrates of carbon [C(H2O)]n

 Carbohydrates  Saccharide
 Most abundant carbohydrates are polysaccharides
 Most important carbohydrate in the body is GLUCOSE
Function of Carbohydrates

 Is our main storage of fuel (Starch ,Glycogen)

 Structural function (Cellulose)
 Provide Cell adhesions between cells (glycosphingolipids)
 Transport of certain substances- Cerrulplasmin (Cu),
Transferrin (Fe)
Function of Carbohydrates

confer biologic specificity on the surface of

animal cells
Blood typing:
Type “A” – N-acetylgalactosamine
Type “B” – D-galactose
Type “AB” – both sugars are present
Type “O” – both sugars are absent

lubricants of skeletal joints

 Hyaluronic acid – in ground substance and in
connective tissue of vertebrates
Functions of Carbohydrates

 as metabolites of glucose, supply precursors for

the synthesis of vital biological substances
 - components of enzymes (glycoproteins)
(Ex. pepsin, pancreatic RNAse, DNAse)
 - as components of hormones (Ex. FSH, TSH)
 - Precursors of DNA, RNA and Ascorbic acid
Definition

Polyhydroxy aldehyde or polyhydroxy ketone or

compound that yield these derivatives on hydrolysis
Hydrolysis
More terms to remember

Aldose – a carbohydrate that contains an aldehyde

group
Ketose- contains a ketone group
Triose- a carbohydrate containing 3 carbon atoms
Tetrose- a carbohydrate with 4 carbon atoms
Aldopentose- 5 carbon atoms with aldehyde group
Ketohexose- 6 carbon atoms with a ketone group
Classification
Monosaccharides

Can not be hydrolyzed to simpler CHO

Classified according to
Whether it contains Aldehyde or Ketone group
Number of carbon atoms
Also includes the polyhydric alcohols(polyols)in
which the aldehyde group or ketone group has been
reduced to an alcohol group
( for weight reduction and diabetics )
Monosaccharides
Oligosaccharides

Contains 2-10 monosaccharide units

Joined together by a glycosidic bond
Subdivided based on the number of monosaccharide
units
Disaccharides
Trisaccharides
Tetrasaccharides
Pentasaccharide
Polysaccharides

Contains more than 10 sugar units

Also called glycans
Maybe linear or branched
Do not exhibit any of the properties of aldehyde or
ketone group
High molecular weight and sparingly soluble in cold
water
Structure of monosaccharide

Glucose is the most important physiologic and

biomedical monosaccharide
It can be represented as
The straight chain structure
Ring/ Cyclic structure
Boat/ Chair form
Structure of a monosaccharide
Isomerism

 Compounds possessing same molecular formula but have different

structures are called ISOMERS
 Aldose- Ketose isomerism (structural isomerism)
 D and L isomerism (enantiomer)
 Optical isomerism
 Epimerism
 Anomerism
 Mutarotation
Stereoisomerism

 Same molecular structure and formula but differ in configuration

 Asymmetric (Chiral) carbon is responsible for stereoisomerism
 Glucose exhibits 4 types
D and L isomerism
Optical isomerism
Epimerism
Anomerism
 Optical isomerism
Optical activity is the capacity of a substance to rotate
a plane of polarized light passing through it
Epimerism

Epimers are sugars which differ with each other with

respect to single carbon, other than the anomeric
carbon
Galactose and Mannose are epimers of glucose
They differ from glucose at C4 and C2 respctively
Anomerism

In aqueous solution, glucose exist mostly as a closed

chain structure
This results in an additional asymmetric carbon
(anomeric carbon)
This leads to formation of two isomers namely
a-D-glucopyranose
b-D-glucopyranose
Anomerism
Anomerism

a- OH grp is
below the plane

b-OH grp is
above the
plane
Mutarotation
Chemical Properties of
Monosaccharides

Monosaccharides have the following important

chemical properties
Furfural formation
Enolization
Oxidation
Reduction
Osazone formation
 Furfural Formation

 Sugar when treated with strong mineral acids like

Conc. Sulfuric acid (H2SO4)
Conc. Hydrochloric acid (HCL)
Conc. Nitric Acid (HNO3)
 They undergo dehydration and lose 3 water molecules to form
furfural derivatives
 The basis for the following tests
Molisch’s test
Seliwanoff’s test
Furfural formation
 Enolization/Tautomerization

Action of an alkaline solution on glucose for several

hours causes it to undergo isomerization to form D-
fructose and D-mannose
This results in formation of a common intermediate-
enediol
The process of shifting of hydrogen atom from one
carbon atom to another to produce enediols is known
as tautomerization
•“Lobry–deBruyn–von-Alberta–
van-Ekenstein transformation”
Oxidation

Oxidation of glucose under proper conditions may

form Sugar acids
Monobasic Aldonic Acid-- oxidation with
Hydrobromous acid
Dibasic saccharic acid or Alderic Acid – oxidation
with nitric acid (HNO3)
Monobasic Uronic acid– oxidized by specific
enzymes
Oxidation
 Oxidation

Glucaric Acid may play a role in the prevention of cancer

Oxidation
5 Min Break
 Reduction

 Aldoses and Ketoses may be reduced by enzymes to its

corresponding polyhydroxy alcohol
 The sugar alcohol function mainly as intermediates in the
minor pathway of carbohydrate metabolism
 Examples are the following
Sorbitol
Mannitol
Dulcitol
Ribitol
Reduction
 Osazone formation

• Used to detect reducing sugars

• The presence of free carbonyl group is essential for osazone
formation
• Osazones are yellow crystalline derivatives of reducing
sugars with PHENYLHYDRAZINE and have a characteristic
crystal structure which can be used for identification and
characterization of different sugars having closely similar
properties
 Osazone Formation
 Osazone formed from Glucose, Fructose and Mannose are
identical because these are identical in their lower four carbon
atoms
 Non-reducing sugars like sucrose cannot form osazone due
to the absence of a free carbonyl group
 The Osazone crystals of some sugars are
Glucosazone- needle shaped
Maltosazone- sunflower petals shaped
Lactosazone – powder puff or tennis ball shaped
Glycoside Formation

 When hydroxyl group on the anomeric carbon of a

monosaccharide reacts with an OH group of another
carbohydrate or non-carbohydrate leads to glycoside
formation
 The bonds joining the monosaccharides are called glycosidic
or glycosyl bonds
 There are two types of glycoside bonds
O-glycosidic bonds
N-glycosidic bonds
 Physiologically important glycosides

Streptomycin (antibiotic)- used as drug for TB

Cardiac glycoside like digoxin and digitoxin are used
to increase muscle contraction and used for
treatment of CHF
Anthacycline glycoside- used to treat wide range of
cancers
Ouabain- inhibits Na-K ATPase and block the active
transport of Na
Cyanohydrin Formation

• Reacting aldose with HCN

• Cyanohydrin is hydrolyzed to an acid and
reduced to an aldehyde
• Extends sugar unit
• Also known as Kiliani-Fischer synthesis
(Kiliani ascension)
Ruff degradation

Series of reactions that removes the reducing

carbon from a sugar and reduces the number of
chiral centers
Reaction involves H2O2 in alkali solution in the the
presence of Fe or Cu salts
 Tests for monosaccharides

Moolisch test- alpha naphtol rxn, general

reaction for CHO
Bial’s test- orcinol-HCl test, test for pentoses
Tollens test- Phloroglucinol –HCl test, test
for pentose and galactose
Seliwanoffs test- resorcinol-HCl, test for
ketohexoses
 Tests for monosaccharides

• Kilianis test- test for deoxysugar

• Barfoeds test- test for monosacharrides
• Moores test – test for CHO that contain a
free sugar group
 Disaccharides

 Consists of two monosaccharide units held by glycosidic bond

 They subdivide based on presence or absence of free
reducing group into
Reducing disaccharides with free aldehyde or keto group
Example- Maltose and Lactose
Non reducing disaccharide without free aldehyde or keto
group
Example-Sucrose
 Maltose

Contains 2 molecules of glucose units

They are linked by a-(1-4) glycosidic linkage
 It is one of the reducing disaccharide which has a
free functional unit
Lactose

 It is present in the milk sugar

 It contains one molecule of galactose and one molecule of
glucose that are linked by b-(1-4) glycosidic linkage
 It is also a reducing disaccharide
 It hydrolyzed into galactose and glucose by the enzyme
lactase in humans
 Source of carbohydrates in breast fed infants
Sucrose

It contains one molecule of glucose and one

molecule of fructose that are linked by a-(1-2)
glycosidic linkage
It is a non-reducing disaccharide
It hydrolyzed into glucose and fructose by enzyme
Sucrase
Isomaltose

Contains 2 molecules of glucose

Linked by a-(1-6) glycosidic linkage
It is derived from the digestion of starch and
glycogen
Hydrolyzed to glucose in the intestinal tract by
isomaltase
Trehalose

Contains 2 molecules of glucose linked by a-(1-1)

glycosidic linkage
Non reducing disaccharide
Found in yeast and fungi
Polysaccharides
(Starch)

Storage of carbohydrates in plants

Homopolymer composed of D-glucose units held by
a-glycosidic bonds
Composed of water soluble amylose (15-20%) and
insoluble amylopectin (80-85%)
 Starch

Chemically, amylose is a long unbranched chain of 200-1000 of

D-glucose units linked by a-(1-4) bonds
 Starch

 Amylopectin, is a branched chain with (1-6) bonds at

branching points and (1-4) bonds everywhere else
 Amylopectin contains few thousand of units looks like a
branched tree (20-30 units/branch
 Hydrolyzed by the enzyme amylase into dextrin, then maltose
and glucose
Dextrins

- Glucose residues linked by α 1,6 linkages

with additional α 1,2 or α 1,3 bonds
- Products of partial or incomplete
hydrolysis of starch
They have free sugar group and thus show
mildly reducing property
Dextrin
 Glycogen

- Highly branched
- Consists of glucose molecules linked by α 1,4
linkages in the chain with branching points every
8 to 12 residues (α 1,6 linkages)
- Animal starch, similar to starch but more
branches
 Cellulose
- Glucose residues joined by β 1,4 linkages
- Major component of vegetable fiber
- Chief constituent of plant cell walls
- Source of bulk in the stool
- Unbranched
- Cannot be digested by humans
- Dec absorption of glucose and cholesterol
- Aids in intestinal mobility (stool softener), prevent constipation
 Inulin
- Consists mainly of fructose units joined by
β 2,1 linkages with a terminal glucose
residue
- Used to determine glomerular filtration
rate
- Readily soluble in water
- Not hydrolyzed by intestinal enzymes
Inulin
 Chitin
- Gives rigidity to the exoskeletons of crabs,
lobsters, shrimps, insects and other
arthropods
- Cell walls of fungi
- Linear polymer of N-acetylglucosamine in β
1,4 linkages
Chitin
 The End
Any Questions?

Sources:

Lecture on slideshare by Ashok Katta “Carbohydrate Chemistry”

Chapter 14, Harper’s illustrated Biochemistry, 29th ed