3-Bch202 Carbohydrates Modified
3-Bch202 Carbohydrates Modified
3-Bch202 Carbohydrates Modified
College of Science
Department of Biochemistry
Chapter 3
Carbohydrates
Notice, you can find two forms of monosaccharides having the same number of carbon atoms
(aldose and ketose)
Monosaccharides (Cont.)
- The simplest monosaccharides is trioses having
3 carbons.
Two trioses are present; glyceraldehyde and
dihydroxyacetone.
Notice, Both can be written C3H6O3 or (CH2O)3
One is aldotriose and the other is ketotriose.
- Positional isomers
with substituent groups on different C-atoms
e.g. 2-Phosphoglycerate and 3-Phosphoglycerate
- cis-trans isomers
Compounds with different conformation around double bonds
H COOH H COOH
Notice, compounds of
this example are not
C C sugar
C C
HOOC H H COOH
A C D D C A
E E
Mirror
One member of an enantiomeric pair will rotate a plane of polarized light in a clockwise direction.
It is said to be dextrorotatory which is labelled (+)
The other member of the pair will rotate the light in a counterclockwise direction.
It is said to be levorotatory which is labelled (-).
Remember
Compound with optical activity means it has chiral carbon
and it can rotate the plane of polarized light as it travels
through it to either right, dextrorotatory (clockwise) or to the
left, levorotatory (anticlockwise)
Do you know the meaning of polarized light and optical activity?
In general, a molecule with n chiral centers can have 2n stereoisomers.
e.g. Glyceraldehyde has 21 = 2;
Aldohexoses, with four chiral centers, have 24 = 16 stereoisomers.
3 Aldose 1 2
4 Aldose 2 4
5 Aldose 3 8
6 Aldose 4 16
3 Ketose 0 --
4 Ketose 1 2
5 Ketose 2 4
6 Ketose 3 8
- Glyceraldehyde is used as a reference for optical isomers because it is the simplest
monosaccharide with an asymmetric carbon. Q1
O H O H
Chiral C C CH2OH
carbon
H- C - OH HO- C - H C O
D-Glyceraldehyde is the isomer that has the hydroxyl group on the RIGHT when the aldehyde group is
at the top in a Fischer projection formula.
It is also dextrorotatory, so it is also D(+)-Glyceraldehyde
L-Glyceraldehyde is the isomer that has the hydroxyl group on the LEFT when the aldehyde group is
at the top in a Fischer projection formula.
It is also levorotatory, so it is also L(-)-Glyceraldehyde
Dihydroxyacetone has only one form. It does not have D nor L form . Explain why? Q2
enantiomers
D & L designate absolute configuration of the asymmetric carbon atom farthest
from the aldehyde or ketone group. Notice: enantiomers are two isomers of
the same sugar
The 6-C aldoses have 4 asymmetric centers. Thus there are 16 stereoisomers (8
D-sugars and 8 L-sugars).
Calculate the number of stereoisomers
Most naturally occurring sugars are D isomers. of glucose and name them?
Enantiomers vs diastereomers
Lehninger, Principles of
Biochemistry, 4th ed.
Quiz
Q2: Explain the meaning of epimer and identify the epimers of (a) D-allose, (b) D-gulose, and (c) D-
ribose at C-2, C-3, and C-4 in the Fig.
HO H H H OH
C C C
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Glucose
• The main source of energy CH2OH
• Binds to other sugars to give O
H OH
disaccharides, oligo and poly
saccharides H
• It is aldo hexose, glucopyranose OH H H
OH
• It is called Dextrose H OH
• (dextro-rotarory) +52.5 (this value
represents the mix of and at equilibrium) -D-Glucose
• i.e it rotates the rout of polarized
light to the right by 52.5 degree
• It is reducing sugar
• It is called also grape sugar
Fructose
• It is Keto hexose
• The most sweet sugar
• It is called levulose (levo rotatory) -92.3
• It is reducing sugar
• It is called also fruit sugar
• It binds to glucose to give sucrose
• Surprisingly, fructose form both pyranose and furanose rings.
• The pyranose form predominantly found when fructose is free in solution while
furanose is predominant in many fructose derivatives.
• β-D-Fructopyranose, found in honey, is one of the sweetest chemicals known.
• The β -D-Fructofuranose form isn't nearly as sweet.
• Heating converts β -pyranose into β -furanose form, reducing sweetness.
• For this reason, corn syrup with high concentration of fructose in β -D-pyranose
form is used as sweetener in cold drinks but not in hot drinks.
Fructose of highest sweet taste is the form of ………………
a- β -D-Fructofuranose b- β -D-Fructopyranose c- -D-Fructofuranose d- -D-Fructopyranose
Galactose
• It does not found free in nature
• Binds to glucose to give lactose
• It is aldo hexose
• It is reducing sugar
• It is epimer to glucose at C-4
• Galactose can be converted in the cell into glucose to be used for
energy production.
• It has an important role in cell communication.
• It is also synthesized by the body and forms part of glycolipids
(carbohydrates-containing lipids), glycoproteins (carbohydrates-
containing proteins) and galactolipids that occur in the brain and
other tissues of most animals.
Ribose
CH OH OH
2 O
OH H
Reactions of simple sugars
The anomeric carbon can react with alcohol, nitrogen of amine or phosphate to form
glycosidic bond
Other carbons in the sugar backbone can react phosphate or with amine to form sugar
Phosphate or sugar amine, respectively.
These modifications give the carbohydrate more characteristics enabling them to serve as
signal molecules or facilitate the metabolism of the carbohydrate.
https://www.youtube.com/watch?v=iuW3nk5EADg
Reducing vs nonreducing sugars
The hemiacetal linkage is weak and can be dissociated to give the open form.
This process makes the carbonyl group available to reduce mild oxidizing agent such as ferric
(Fe+3) or cupric (Cu+2) ion and the carbonyl carbon is oxidized to a carboxyl group plus
ferrous (Fe+2) or cuprous (Cu+) .
This property is the basis of Fehling’s reaction, a test for the presence of reducing sugar.
By measuring the amount of oxidizing agent reduced by a solution of a sugar, we estimate the
concentration of that sugar.
Sugars with a free or potentially free aldehyde or ketone group (hemiacetal or
hemiketal) have reducing properties and are called reducing sugars.
So, all monosaccharides are reducing sugars.
In case of converting all the hemiacetal or hemiketal linkage to the strong acetal or ketal, the
sugar loses the reducing ability and is called nonreducing sugar.
Cu2O
Benedict’s
solution
- Oxidation of aldoses (using Fehling reagent)
The presence of the hydrogen atom in the aldehyde group gives reducing properties to the
aldehyde molecule.
Aldehydes are easily oxidized by mild oxidizing agents such as Fehling’s reagent to
carboxylic acids
Thus, aldoses are reducing agents.
Any sugar that has a free aldehyde group is referred to as a reducing sugar.
The product name is made by changing the –ose ending to –onic acid (-onate)
Glucose gluconic acid or gluconate
Tests for reducing sugars: Fehling’s reaction [Cu(II) Cu(I)]
https://www.youtube.com/watch?v=iuW3nk5EADg
- Oxidation of ketoses (using Fehling reagent)
Ketones do not have such reducing properties of the aldehyde group due to the
lack of H attached to C=O and are not oxidized under similar conditions.
BUT, fructose reduces such reagents even though it contains no aldehyde group.
Reduction occurs because the reagents are basic solutions and fructose is readily
isomerized to a mixture of aldoses (glucose and mannose) under basic
conditions.
2-Esterification
The most important biological esters of carbohydrates are phosphate esters.
In the cell, phosphate esters are produced NOT by using the very acidic
phosphoric acid, but most often by transfer of phosphate group from ATP to
carbohydrate hydroxyl group, a reaction catalyzed by enzymes called kinases.
2-Esterification-Phosphorylation
The addition of phosphoryl groups is
common in sugar metabolism.
Glucose in converted in the glycolysis
pathway to glucose 6-phosphate, which
undergo a series of reactions, all of them
contain phosphate group including fructose
6-Ph, Fructose 1,6-diPh, Glyceraldehyde 3-
Ph, Dihydroxyacetone Ph., 6-
Phsphoglycerate and PhosphoinolPyruvate.
H O H H O H
The amino group of glucosamine may be H
OH H
H
OH H
acetylated, as in N-acetylglucosamine. OH OH OH O OH
H NH2 H N C CH3
H
-D-glucosamine -D-N-acetylglucosamine
N-acetylneuraminate (N-acetylneuraminic
acid, also called sialic acid) is often found as O H
After glycosidic bond formation, the anomeric carbon involved in bond formation
is stabilized and the bond converts to acetal or ketal (strong bond) with no
potentially free aldehyde or keto groups.
The glycosidic bond has direction and orientation and could affect the reducing
character of the sugar (see the disaccharides coming next lecture).
Glycosylation Reaction
There are several types of glycosylation, although the first two are the
most common.
In N-glycosylation, sugars are attached to nitrogen, typically on
the amide side-chain of asparagine.
In O-glycosylation, sugars are attached to oxygen, typically
on serine or threonine but also on non-canonical amino acids such
as hydroxylysine & hydroxyproline. Also bond between monosaccharides to
form oligosaccharides and polysaccharides is o-glycosylation.
In P-glycosylation, sugars are attached to phosphorus on a phosphoserine.
In C-glycosylation, sugars are attached directly to carbon, such as in the
addition of mannose to tryptophan.
In glypiation, is the covalent bond of Glycosyl Phosphatidyl Inositol (GPI)
anchor and is a common post-translational modification that localizes proteins
to cell membranes. Glycolipid is attached to the C-terminus of a polypeptide,
serving as a membrane anchor.
N-linked glycosylation
Sugar molecules can be attached to asparagine or glutamine by N-linked glycosylation
-D-N-acetylglucosamine
O-linked oligosaccharide chains of
glycoproteins vary in complexity.
O-linked oligosaccharides have roles in recognition, interaction, and enzyme
regulation.
N-acetylglucosamine (GlcNAc) is a common O-linked glycosylation of protein
serine or threonine residues.
Many cellular proteins, including enzymes & transcription factors, are regulated by
reversible GlcNAc attachment.
Often attachment of GlcNAc to a protein OH alternates with phosphorylation, with
these 2 modifications having opposite regulatory effects (stimulation or
inhibition).
O-linked versus N-linked glycosidic bond
O-glycosidic bond
N-glycosidic bond
amine (NH) substitutes for OH,
- N reacts with anomeric C
- seen in formation of nucleic acids
- asparagine can be used to make glycoprotein
N-Glycosides can substitute for hydroxyl groups and react at the anomeric carbon center of carbohydrates
This linkage is called an N-glycosidic bond .
This type of bond is of paramount importance in the construction of nucleotides such as ATP and in the
nucleic acids RNA and DNA
Glucose in the blood and the glycated HbA1c
eAG (estimated average
glucose)
hemoglobin (mmol/
% (mmol/L) (mg/dL)
mol)
Glucose is the main sugar in our diet and in the body. 5 31 5.4 (4.2–6.7) 97 (76–120)
The normal blood glucose is 70-110 mg%. 6 42 7.0 (5.5–8.5) 126 (100–152)
Blood glucose reacts with the N-terminal of the beta 7 53 8.6 (6.8–10.3) 154 (123–185)
chain of the hemoglobin nonenzymaticaly. 8 64 10.2 (8.1–12.1) 183 (147–217)
This glycosylation (glycation) reaction forms a Schiff 9 75 11.8 (9.4–13.9) 212 (170–249)
base which is itself converted to 1-deoxyfructose. 10 86 13.4 (10.7–15.7) 240 (193–282)
In diabetic patients, the blood glucose levels are 11 97 14.9 (12.0–17.5) 269 (217–314)
12 108 16.5 (13.3–19.3) 298 (240–347)
high, glucose molecules attach to the hemoglobin in red
13 119 18.1 (15–21) 326 (260–380)
blood cells. So, the glycated hemoglobin is higher.
14 130 19.7 (16–23) 355 (290–410)
The level of glycated hemoglobin within the red cell,
15 140 21.3 (17–25) 384 (310–440)
therefore, reflects the average level of glucose to which
16 151 22.9 (19–26) 413 (330–480)
the cell has been exposed during the RBCs life-cycle (120 17 162 24.5 (20–28) 441 (460–510)
days). 18 173 26.1 (21–30) 470 (380–540)
So, measuring glycated hemoglobin in the form of plasma 19 184 27.7 (23–32) 499 (410–570)
glucose concentration assesses the effectiveness of
https://en.wikipedia.org/wiki/Glycated_hemoglobin
therapy by monitoring long-term serum glucose regulation
during 3 months.
Sugar derivatives
CH2OH COOH CHO
H C OH H C OH
H C OH
HO C H HO C H
H C OH
H C OH H C OH
H C OH
H C OH H C OH
CH2OH
CH2OH COOH
D-ribitol D-glucuronic acid
D-gluconic acid
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Disaccharides Contain a Glycosidic Bond
Disaccharides (such as maltose, lactose, and sucrose)
consist of two monosaccharides joined covalently by an
O-glycosidic bond, which is formed by dehydration
(removal of H2O), a hydroxyl group of one sugar and
hydrogen from OH of other sugar.
This reaction form an acetal from a hemiacetal.
Glycosidic bonds are readily hydrolyzed by acid but resist
cleavage by base.
Thus, disaccharides can be hydrolyzed to yield their free
monosaccharide components by boiling with dilute acid.
Maltose
It is also called maltobiose or malt sugar.
The disaccharide maltose contains two D-glucose residues joined
by a O-glycosidic linkage between C-1 (the anomeric carbon)
of one glucose residue and C-4 of the other.
Because the disaccharide retains ONE free anomeric carbon
maltose is a reducing sugar.
The configuration of the anomeric carbon atom in the glycosidic
linkage is α-(14).
The glucose residue with the free anomeric carbon is capable of
existing in α- and β–pyranose forms.
Non-reducing reducing
Isomaltose
How you can define the reducing ability from the sugar name without looking for the chemical structure?
Sucrose
Sucrose (table sugar or cane sugar) is a disaccharide of glucose and fructose.
It is formed by plants but not by animals.
In contrast to maltose and lactose, sucrose contains no free anomeric carbon atom;
the anomeric carbons of both monosaccharide units are involved in the glycosidic bond
(, 12).
So, sucrose is therefore a non-reducing sugar.
What are the changes that appear on sucrose when treated with acid and heating?
3-Glucose is ……………….
A- aldohexose B- dextrose C- Grape sugar D- all of the above
A- B- C- D-
4-The sugars lactose, maltose and sucrose all belong to which category of carbohydrates?
A-Monosaccharides B- Disaccharides C- oligosaccharides D- polysaccharide
Quiz
How many different oligosaccharides can be made by linking one
glucose, one mannose, and one galactose? Assume that each sugar is
in its pyranose form. Compare this number with the number of
tripeptides that can be made from three different amino acids.
Three amino acids can be linked by peptide bonds in only six different
ways. However, three different monosaccharides can be linked in a
plethora of ways.
- linear or branched manner,
- α or β linkages,
- with bonds between C-1 and C-3, between C-1 and C-4, between C-1 and
C-6, and so forth.
Consequently, the number of possible trisaccharides greatly exceeds the
number of tripeptides.
Stryer
Quiz
Q: A disaccharide, which you know to be either maltose or
sucrose, is treated with Fehling’s solution, and a red color is
formed. Which sugar is it, and how do you know?
Ans: Maltose is the reducing sugar;
sucrose has no reducing (oxidizable) group, as the anomeric
carbons of both monosaccharides are involved in the glycosidic
bond.