Carbohydrates

Chemistry
Dr. ZAID HEZAM AL-HAMODI
Ph.D
Assistant Professor
2019/2020
 Program of study (course outline)
Carbohydrates:
a) Monosaccharide.
b) Monosaccharide sugars derivatives
c) Disaccharides.
d) Oligosaccharides
e) Polysaccharides, homopolysaccharides,
hetropolysaccharides sugars derivatives.
 INTENDED LEARNING OUTCOMES (ILOS)
At The End of Course Students Must Know the Following:
1. Carbohydrates definition.
2. Medical Importance of Carbohydrates.
3. Carbohydrates classification.
4. Monosaccharide classification, types, structures & properties.
5. Nomenclature of Carbohydrates .
6. Monosacchrides derivatives: sugar alcohols, sugar acids, deoxy
sugar, amino sugars & amino sugar acids.
7. Disaccharides definition, types, structures & properties.
8. Polysaccharides definition, classification, types of
homopolysaccharides & heteropolysaccharides & their functions.
 Carbohydrates Chemistry
Carbohydrates “CHO” (glycans):
 are polyhydroxy aldehydes or ketones or compounds
that give polyhydroxy aldehydes or ketones on hydrolysis.
Medical importance of carbohydrates
1) Major source of energy in the body (1g of CHO gives 4 Kcal).
2) Storage of energy polysaccharides serve as energy
storage (glycogen) in liver & muscles.
3) Physiological anticoagulant (Heparin).
4) Important component of nucleic acids DNA & RNA
(Deoxyribose & ribose).
5) Hyaluranic acid serves as lubricant in synovial fluid
of the joints.
6) Some glycosides (CHO derivative from plants) are
important drugs, such as glycoside of digitalis used for
treatment of heart diseases & streptomycin used as
antibiotic.
Medical importance of carbohydrates
7) L-Fucose is main component of blood group (A,B,O, Rh)
8) Inulin (homopolysaccharide) is used to evaluate renal
function.
9) Agar (polysaccharide) is used for preparation of
bacterial & fungal culture media.
10) Manitol (sugar alcohol of mannose) used as diuretic.
11) Lactulose used as a prebiotic & in treatment of
constipation & hepatic encephalopathy.
12) Xylitol is a tooth-friendly (prevents dental caries).
 Classification of carbohydrates
According to the number of simple sugar units they
contain can be classified into 4 groups:
1) Monosaccharides (contain a single unit)
2) Disaccharides (contain 2 sugar units)
3) Oligosaccharides (contain 2-10 sugar units)
4) Polysaccharides (contain ˃ 10 sugar units as polymers)
 Monosaccharides
 The simplest unit of CHO.
 Its name comes from Greek word (mono=single & sacchar=sugar)
 Its general formula is Cn(H2O)n, (n= # of C “3-9”).

Classification of monosaccharides
1) According to the # of C atoms they contain:
C# Type Examples
3 Triose Glyceraldehyde & Dihydroxyacetone
4 Tetrose Erythrose & Erythrulose
5 Pentose Ribose, Xylose, Arabinose, lyxose & xylulose
6 Hexose Glucose, galactose, mannose & fructose
7 Heptose Sedoheptulose
9 Nonose Neuraminic acid
 Classification of monosaccharides
2) According to the type of carbonyl group they contain
(aldehyde or ketone):
1) Aldose: e.g., Glucose, Galactose, mannose, ribose, Glyceraldehyde.
2) Ketose: e.g., Fructose, ribulose, dihydroxyacetone, erythrulose.
3) According to both the type of carbonyl group & # of C atoms:
a) Aldotriose (Glyceraldehyde) & ketotriose (Dihydroxyacetone).
b) Aldotetrose (Erythrose) & ketotetrose (Erythulose).
c) Aldopentose (Ribose) & ketopentose (Ribulose).
d) Aldohexose (Glucose) & ketohexose (Fructose).

 N.B.: All monosacch. considered triose glyceraldehyde derivatives.

 Nomenclature of monosaccharides
In general CHO have been given non-systemic names,
although the suffix -ose is generally used.
 Monosaccharides are named according to these rules:
The number of C as the variable prefix
followed by –ose as the suffix.
Carbons are numbered from the top of sugar.
Aldehyde or ketone group is on the C with
the lowest possible number & the sugar with
aldehyde group called aldose, & the sugar
with ketone group called ketose.
Example: Hexose, Aldose, Aldohexose, glucose
 Asymmetric or chiral carbon
 C atom attached with 4 different groups determines the
number of isomers of sugar & optical activity

L-glucose D-glucose
 Important monosaccharides
1) D-Glucose (Dextrose, C6H12O6):
 Its name comes from the Greek word glukus = sweet
• The most predominant sugar in human body
D-Glucose
• The major source of energy in mammals.
• The sole source of energy for brain & RBCs.
• Known as blood sugar, grape sugar & dextrose
• Present in honey & fruits
α-D-Glucose (Pyranose)
• Obtain by hydrolysis of:
o Sucrose, maltose & lactose, &
o Starch & glycogen

Haworth formula open chain formula

 Important monosaccharides
2) D-Fructose (Ketohexose, C6H12O6 )
 Its name comes from the Latin word fructus = fruit
• The sweetest of monosaccharides,
• Present in honey & fruits
• The main sugar of semen that used by D-Fructose
sperms as energy source.
• Known as fruit sugar, fetal blood
• Obtained by hydrolysis of sucrose & inulin
& change to glucose in liver & intestine.
α-D-Fructose (furanose)
 Important monosaccharides
CHO CHO
3) D-Galactose (C6H12O6 ):CHO
H C OH HO C H H C OH
 Its name comes from the Greek word galact = milk
HO C H HO C H HO C H
• Not found free in nature, H C OH H C OH HO C H
• Found as a component of Hlactose
C OH
in milk.
H C OH H C OH
• Obtained by hydrolysis of lactose
CH2&
OHchange to
CH2OH CH2OH
glucose in liver Glucose Mannose Galactose

4) D-Ribose:
• Found in the backbone structure of nucleic acid
RNA & some coenzymes, e.g., FAD,
NADH, ATP, & coenzyme A.
5) D-Mannose:
 A component of glycoproteins &
changed to glucose in the body.
Cyclic (ring) structure of monosaccharides
Hawarth formula: all monosacchrides with at least 4C
atoms exist predominantly as cyclic structure.
• Ring formation occurs in aqueous solution or solids because
aldehyde group (C1 in aldose) & ketone group (C2 in ketose)
react reversibly with OH groups (C4 or C5) present in the same
sugar to form cyclic hemiacetals.
Anomeric carbon: the carbonyl group that attached
with 4 different groups (asymmetric) called the anomeric C.
 According to the position of OH group around the anomeric
C, the sugar called α- or β-sugar.
• if -OH group is below the plane of the ring, the sugar called
α-sugar & if it’s above, the sugar called β-sugar, so that the
α-Glu & β- Glu called anomers (isomers obtained from the change
of position of OH group attached to the anomeric C of the same sugar).
β-D- Glucose, boat form β-D-Glucose, chair form

chair form is more stable

than boat form
 Properties of monosaccharides
1) Water soluble, crystalline & unaffected by digestive enzymes.
2) Have one asymmetric C or more except dihydroxyacetone
3) All monosaccharides have optical activity except dihydroxyacetone.
 Optical activity: the ability of substance that have 1 asymmetric C or
more to rotate a beam of polarized light either to the right or left.
• If the rotation is to the right called dextrorotatory (+ or d) & if it’s to
the left called levorotatory (- or L).
4) Enantiomers are a type of isomers designated as “D” & “L” isomers
that are mirror images of each other & differ in the configuration
around the asymmetric C before the last C atom. e.g D & L glucose.
 Different possible isomers of Glucose:
1. D & L forms of glucose (Enantiomers).
2. α & β forms of D-Glucose (Anomers).
3. Pyranose & Furanose forms of D-Glucose. (Functional group isomers)
4. Epimers of Glucose as mannose & galactose.
5. Aldo-Keto isomers as glucose & fructose.
 Properties of monosaccharides
5) Epimers are sterioisomers that differ in the position of OH
group at only one of their asymmetric C atom other than
before the last (sub-terminal) C atom. e.g:
• D-Glucose & D-Galactose are C4 epimers.
• D-Glucose & D-Mannose are C2 epimers.
• D-arabinose is an epimer of D-ribose at C2.
• D-xylose is an epimer of D-ribose at C3.
CHO CHO CHO CHO CHO CHO

HO C H H C OH HO C H H C OH
H C OH 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 HO C H
H C OH H C OH H C OH
H C OH H C OH H C OH
CH2OH CH2OH CH2OH
CH2OH CH2OH CH2OH
Ribose Arabinose Xylose Glucose Mannose Galactose
 Properties of monosaccharides
6) Mutarotation: is a change in the optical rotation of polarized
light that passes through a freshly prepared solution of sugar
due to presence of α & β forms of sugar.

Racemic mixture is a mixture of equal amount of 2 optically

active molecules of the same sugar, one is rotate polarized light to
the right & the other to the left & it’s optically inactive because the 2
molecules have opposite direction & equal rotation angle.
 In other word it’s an equal amount of enentomers. Examples:
1. D (+ or d) Glucose & L(- or l) Glucose (does not occur in nature).
2. D (- or l) Fructose & L(+ or d) Fructose (does not occur in nature).
 Monosacchrides derivatives
1) Sugar alcohols
 carbonyl group → reduced to alcohol group.
 Glucose is reduced to sorbitol (glucitol): used as a sugar substitute
for diabetics & prevent foods dehydration.
1) Mannose is reduced to mannitol: used as osmotic diuresis.
2) Fructose is reduced to mannitol & sorbitol.
3) Galactose is reduced to galacticol (dulcitol).
4) Ribose is reduced to ribitol: a constituent of vit B2 & FAD.
5) Xylose is reduced to xylitol: a tooth-friendly, prevents dental caries
(non-fermentable sugar alcohol) .
• It used in making toothpaste, mouth washes & as a sweetener in chewing gums.
6) Inositol is derived from glucose.
• Myoinositol: present in high conc. in heart & muscles (muscles sugar).
• Component of a phospholipids (lipositol): mobilization of fat from liver
• A precursor of 2nd messenger (PI3): important in hormone action.
 2) Sugar acids
 Produced by oxidation of aldehyde group, or last OH group or both.
a) Aldonic acids: aldehyde group of aldose is converted to a carboxyl
group to form aldonic acid.
 Glucose is oxidized to gluconic acid, mannose to mannonic acid &
galactose to galactonic acid.
b) Uronic acids: the last OH C is oxidized to a COOH group, forming
uronic acid.
 Glucose is oxidized to glucuronic acid. (used by the body for
conjugation with insoluble molecules to make them soluble in water).
 Aldonic & uronic acids can be formed in the body by enzymatic oxidation.
c) Aldaric acids : are dicarbocylic acids produced by oxidation of both
ends of aldose (aldehyde group & last OH C).
 Glucose is oxidized to glucaric acid (glucosaccharate) & galactose to
galactarate (mucic acid)
 3) Deoxy sugar
• Sugars that have a H group instead of a OH group.
1. D-2-deoxyribose
• Found in the backbone structure of DNA.
2. L-Fucose (6-deoxy-L-galactose)
• Found as a constituent of glycoprotein & blood group substances.
3. L-Rhamnose (6-deoxy-L-mannose)
• Seen in many glycosides (molecules in which a sugar is bound to non-CHO moiety).
 4) Amino sugars
 Sugars in which amino group (-NH2) replaces the OH group on
the 2nd C atom.
1. Glucosamine
• Found in blood group substances, glycoprotein hormones, heparin &
hyaluronic acid & it’s used as safe therapy of osteoarthritis
(degenerative arthritis).
• Its amino group may be further acetylated → N-acetyl-glucosamine
2. Galactosamine
• Present in chondroitin sulphate of cartilage, bone & tendons & it’s a
constituent of glycoprotein hormones.
• Its amino group → may be further acetylated → N-acetyl-galactosamine.
3. Mannosamine
• Present in neuraminic & sialic acids (N-acetyl neuraminic acid).
• Its amino group may be further acetylated → N-acetyl-manosamine.
 5) Amino sugar acids
• Formed by addition of acids to amino sugars.
 Aaddition of pyruvic acid to mannosamine gives neuraminic acid &
addition of pyruvic acid to N-acetyl-manosamine gives N-acetyl
neuraminic acid (sialic acid).
• Neuraminic & sialic acids are component of glycosamino-glycans,
glycoprotens & gangliosides.

N-acetyl-neuraminic acid (sialic acid)

 Disaccharides
 are O-glycosides that are composed of 2 monosaccharides that
linked together by glycosidic bond.
• Its general formula is Cn(H2O)n-1.

1) Lactose: β-D-galactose & β-D-glucose linked by β-(1→4) gly. bond.

2) Maltose: 2 α-D-glucose linked by α-(1→4) gly. bond.
3) Sucrose: α-D-glucose & β-D-fructose linked by α-(1→2) gly bond.
4) Lactulose: β-D-galactose & β-D-fructose linked by β-(1→4) gly. bond.
5) Trehalose: 2 α-D-glucose linked by α-(1→1) gly. Bond.
 1) Lactose (milk sugar)
 The Latin word lact = milk, it’s fund in milk.
• Consist of β-D-galactose & β-D-glucose linked together by β-(1→4)
glycosidic bond.
• Synthesized by mammary glands during lactation,
• It’s the best food for infants, (the least sweet sugar: baby can nurse a large amount of mother’s
milk without getting his appetite lost).

 It has a free anomeric C in glucose residue, it has the following properties:

1) Present in α & β forms.
2) Undregoes mutarotation (changes of α to β form & vice versa)
3) It’s reducing sugar (any sugar contain a free aldehyde or ketone group can reduce
certain reagents, “lactose contain free aldehyde group”).
4) It can form characteristic osazone crystal (Cotton ball shape)
CH2OH CH2OH
O O
H OH ..... H
OH
H H
1 O 4
H OH H
OH H H ..... OH
H

H OH H OH
-Galactose Glucose
and Lactose
2) Maltose (malt sugar)
 Produced during starch digestion by α-amylase.
 Not found free in nature (Produced during starch digestion by α-amylase)
• Consist of 2 molecules of α-D-glucose linked together by α-
(1→4) glycosidic bond.
 It has a free anomeric C in glucose residue, so it has the
following properties:
1) Present in α & β forms.
2) Undregoes mutarotation.
3) It’s reducing sugar
4) It can form characteristic
osazone crystal (Rosette shape).
3) Sucrose (cane sugar, beet sugar or table sugar)
• The most abundant disaccharides in nature.
• The French word sucre = sugar.
• Found in sugar cane & beet sugar & some fruits.
• Consist of α-D-glucose & β-D-fructose linked together by α-
(1→2) glycosidic bond.
 It doesn’t has a free anomeric C because the anomeric C of
both the α-D-glucose (C # 1) & β-D-fructose (C # 2) units
are involved in formation of the α-(1→2) glycosidic bond,
so that, sucrose has the following properties:
1) Doesn’t Undrego mutarotation.
2) It’s non-reducing sugar.
3) can't form osazone crystal.
4) lactulose
• It’s a synthetic disaccharide & produced from lactose by
isomerization of glucose to fructose.
• It consist of β-D-galactose & β-D-fructose linked together by β-
(1→4) glycosidic bond.
• It can't be digested by human or animal enzymes.
• It’s used in the treatment of constipation (due to the laxative &
osmotic action of lactulose) treatment of hepatic encephalopathy
(elimination of NH3) & acts as a prebiotic.

5) Trehalose
• Formed by 2 molecules of α-D-glucose linked together by
α-(1→1) glycosidic bond, so it’s non-reducing sugar.
• It’s synthesized by fungi & plants & some animals.
• Used in organ protection solution for organ transplants.
 Polysaccharides
 are polymers of ˃10 units of monosaccharides.
• They’re classified into homo & hetero polysaccharides.
a) Homopolysaccharides:
 are polysaccharides consist of 1 type of monosaccharide units
(Starch, Glycogen, Cellulose, Inulin).
1) Starch
• It’s the most important food source of CHO for human.
• Produced by all green plants (Potatoes, wheat & rice).
• It consist of 2 polysaccharides amylose & amylopectin.
 1) Starch
a. Amylose: about 15-20% of starch & composed of long tight
helices, unbranched chains of D-glucose residues that are
linked to each other by α-(1→4) gly bond.
b. Amylopectin: about 80-85 % of starch, it’s a branched polymer
of D-glucose residues containing both α-(1→4) & α-(1→6) gly bonds
(α-(1→6) branch points occur every 20-25 glucose residues & prevent helix formation)

Properties of starch
1. It’s a white, tasteless & odorless powder.
2. Insoluble in cold water.
3. Gives blue color with iodine test.
 CH2OH CH2OH

O O
H H H
H H
H
4 1 4 1
OH H OH
O O
O
H OH H OH

CH CH2OH
CH2OH CH2OH 62
O O
O O H H H
H H H H
H H H
H H 1
4 1 4 H 1 4 OH
4 H 1 OH OH
OH O
O O
O O
H OH H OH
H OH H OH n
Amylopectin

Amylose
2) Glycogen (animal starch)
• The major form of animals storage polysaccharide.
• Found mainly in the liver (represent ≈10% of liver mass) &
skeletal muscle (about 1-2% of muscle mass).
• Similar to amylopectin, but it has many branched points &
short branches
• It gives red color with iodine test.
3) Cellulose
 It’s the most abundant of CHO & organic substances on earth.
• About 33 % of plant matter is cellulose.
• A polymer of linear nonbranching β-D-glucose, linked by β-(1→4) gly
bonds.
• There’re no enzymes in human or animals that are able to hydrolyzed
the -(1→4) gly bond of cellulose but some animals can hydrolyze
cellulose to obtain glucose by some bacteria (has cellulase enzyme)
present in their gut.
Properties of cellulose
1) Tasteless & odorless 2) Insoluble in water & most organic solvent
3) Structural material of plant 4) Gives no color with Iodine test
4) Inulin
 A polymer of D-fructose linked together by -(2→1)-gly bonds
• Found in of onion, garlic & roots of some plants.
• It’s used to measure renal function & acts as a prebiotic.

5) Dextrins
 A polymers of D-glucose units linked by α-(1→4) or α-(1→6) gly
bonds & produced by the hydrolysis of starch.
• Used in infant feeding & as glues in postage stamp & envelope adhesive
6) Dextran
• A branched polymer of D-glucose linked by α-(1→6) gly bonds in
linear chain & by α-(1→3) gly bonds in branches.
• It’s synthesized from sucrose by certain bacteria.
• Dental plaque is rich in dextran.
• Used as plasma expander (increased blood volume), when given
intravenous, in case of haemorrhage & prevent thrombosis.
7) Agar
• A polymer of galactose, present in sea weeds.
• Used as laxative & for preparation of bacterial & fungi culture media
& electrophoretic separation.
b) Heteropolysaccharides
 A polymer consisting of 2 or more different monosaccharides
 There are 3 types
1) glycosaminoglycans,
2) proteoglycans,
3) glucoproteins
1) Glycosaminoglycans (mucopolysaccharides) (GAGs)
 are linear polymers with disaccharide repeating units.
 These units consist of: acidic and amino sugar
1) Hyaluronic acid
• It’s the most abundant GAGs in the synovial fluid of the joints &
vitreous humor of the eye.
• Found in connective tissues & skin.
 Functions:
1. Acts as a lubricant in joints.
2. Responsible for the resilience of cartilage.
3. Involved in tissue repair.
4. Has a role in movement & proliferation of cells.
2) Chondroitin sulphate A & C
• Present in cartilage, cornea of the eye, tendons, ligaments,
bones, & connective tissue matrix.
 Functions
• An important structural component of cartilage & provides much of
its resistance to compression.
• Used as dietary supplement for treatment of osteoarthritis.
3) Keratan sulfate
• Found in cornea, cartilage & intervertebral disks.
 Functions
• Act as a cushion to absorb mechanical shock.
• Has a role in corneal transparency (by maintenance a level of
hydration of cornea tissue).

4) Dermatan sulfate
• Found mostly in skin, also in blood vessels, heart valves,
tendons & lungs.
 Functions:
1. Has a role in wound repair.
2. Acts as anticoagulant (it is called β-heparin).
3. Has a role in resistance to infectious disease.
5) Heparin (α-Heparin)
• Produced by mast cells of liver, kidney, lung & skin.
 Functions:
1. Acts as anticoagulant (activation of antithrombin III that inhibits the
intrinsic pathway of blood clotting).
2. Activates LPL to clear the turbid plasma from the absorbed lipids
after meals.
2) Proteoglycans:
 are heavily glycosylated (contain 95 % CHO) protein chains
consist of a core protein & 1 or more covalently attached
glycosaminoglycan chains (hyaluronic acid, chondrotin sulfate,
keratan sulfate, dermatan sulfate, heparin).
• There’re many types of them occur in the connective
tissues, the largest type are aggrecan (the major type in cartilage)

Funcions
1. Act as a constituent of extra-
cellular matrix, interact with
collagen & elastin to provide
elasticity & support to tissue.
2. Act as a barrier in tissues.
3. Act as lubricant in joints.
3) Glycoprotein (mucoproteins):
 are proteins that are covalently linked to CHO (1 or more oligosaccharide chains) by
O- or N-linkages.
• Their CHO content varies from 1% (in collagen) to 85% (in ABO blood group
substances).
• Their CHO are mannose, galactose, N-Acetylglucosanine, N-
Acetylgalactosamine, arabinose, xylose, L-fucose & sialic acids.
• They occur in cells in both soluble & membrane-bound form & in extra-
cellular fluids.
Functions: Acts as:
1. metal-transport proteins (transferin, ceruloplasmin).
2. a component of the blood clotting factors.
3. enzymes (RNase).
4. lubricant & protective agent (mucins).
5. component of some hormones (TSH).
6. component of structural molecule (collagens).
7. component of immunoglobulins (antibodies).
8. component of the ABO blood group substances.
9. cell receptors.
 Proteoglycans Glycoproteins

Carbohydrate content 95 % (higher) 1-85 % (lower)

Glycosaminoglycans Oligosaccharides

Unbranched branched

Presence of sulfate and uronic acid Present Absent