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
