Ministry of Public Health of Ukraine

Ukrainian Medical Stomatological Academy

Department of biological and bioorganic chemistry

Carbohydrates. Structure and functions of di- and

polysaccharides

Assoc. Prof. Bilets M.V.

 Lecture plan

 Structure and properties of sucrose, lactose, maltose.

 Classification of polysaccharides.
 Structure, biological role of starch.
 Structure and biological role of glycogen.
 Structure and biological role of cellulose.
 Heteropolysaccharides. Glycosaminoglycans. Proteoglycans.
 Disaccharides
There are two functionally different classes of disaccharides:
 Disaccharides (C12H22O11) are sugars composed of two
Reducing disaccharides, in which one monosaccharide, the reducing sugar of the
monosaccharide units that are joined by a carbon–oxygen-carbon
pair, still has a free hemiacetal unit that can perform as a reducing aldehyde group;
linkage known as a glycosidic linkage. This linkage is formed
lactose, maltose and cellobiose are examples of reducing disaccharides, each with
from the reaction of the anomeric carbon of one cyclic
one hemiacetal unit, the other occupied by the glycosidic bond, which prevents it
monosaccharide with the OH group of a second monosaccharide.
from acting as a reducing agent. They can easily be detected by the Fehling's or
Tollens' reagents.
Non-reducing disaccharides, in which the component monosaccharides bond
 The disaccharides differ from one another in their through an acetal linkage between their anomeric centers. This results in neither
monosaccharide constituents and in the specific type of monosaccharide being left with a hemiacetal unit that is free to act as a reducing
glycosidic linkage connecting them. There are three common agent. Sucrose and trehalose are examples of non-reducing disaccharides because
disaccharides: maltose, lactose, and sucrose. their glycosidic bond is between their respective hemiacetal carbon atoms. They
do not react with Fehling's Tollens' reagents.

http://www.chups.jussieu.fr/polys/biochimie/SGLbioch/POLY.Chp.1.5.h
tml https://chem.libretexts.org/Courses/Sacramento_City_College/SCC%3A_Chem_309_-
_General_Organic_and_Biochemistry_(Bennett)/Text/14%3A_Carbohydrates/14.6%3A_Disaccharides
 Maltose

 Maltose occurs to a limited extent in sprouting grain. It is

formed most often by the partial hydrolysis of starch and
glycogen. Maltose is about 30% as sweet as sucrose. The
human body is unable to metabolize maltose or any other
disaccharide directly from the diet because the molecules are
too large to pass through the cell membranes of the intestinal
wall.
 In the body, hydrolysis reactions are catalyzed by enzymes
such as maltase. Hydrolysis of maltose produces two
molecules of D-glucose.
 Maltose is a reducing sugar. Thus, its two glucose molecules
must be linked in such a way as to leave one anomeric
carbon that can open to form an aldehyde group. The
glucose units in maltose are joined in a head-to-tail fashion
through an α-linkage from the first carbon atom of one
glucose molecule to the fourth carbon atom of the second
glucose molecule (that is, an α-1,4-glycosidic linkage. The
bond from the anomeric carbon of the first monosaccharide
unit is directed downward, which is why this is known as an
α-glycosidic linkage. The OH group on the anomeric carbon
of the second glucose can be in either the α or the β position

https://chem.libretexts.org/Courses/Sacramento_City_College/SCC%3A_Chem_309_-
_General_Organic_and_Biochemistry_(Bennett)/Text/14%3A_Carbohydrates/14.6%3A_Disaccharides
 Lactose

 Lactose is known as milk sugar because it occurs in the milk

of humans, cows, and other mammals. In fact, the natural
synthesis of lactose occurs only in mammary tissue, whereas
most other carbohydrates are plant products. Human milk
contains about 7.5% lactose, and cow’s milk contains about
4.5%. This sugar is one of the lowest ranking in terms of
sweetness, being about one-sixth as sweet as sucrose.
 Lactose is a reducing sugar composed of one molecule of D-
galactose and one molecule of D-glucose joined by a β-1,4-
glycosidic bond (the bond from the anomeric carbon of the
first monosaccharide unit being directed upward). The two
monosaccharides are obtained from lactose by acid
hydrolysis or the catalytic action of the enzyme lactase.
 Many adults and some children suffer from a deficiency of
lactase. These individuals are said to be lactose intolerant
because they cannot digest the lactose found in milk. A more
serious problem is the genetic disease galactosemia, which
results from the absence of an enzyme needed to convert
galactose to glucose.

https://chem.libretexts.org/Courses/Sacramento_City_College/SCC%3A_Chem_309_-
http://www.chups.jussieu.fr/polys/biochimie/SGLbioch/POLY.Chp.1.5.html _General_Organic_and_Biochemistry_(Bennett)/Text/14%3A_Carbohydrates/14.6%3A_Disaccharide
 Sucrose

 Sucrose, is known as beet sugar, cane sugar, table sugar, or simply

sugar.
 The sucrose molecule is unique among the common disaccharides in
having an α-1,β-2-glycosidic (head-to-head) linkage. Because this
glycosidic linkage is formed by the OH group on the anomeric carbon
of α-D-glucose and the OH group on the anomeric carbon of β-D-
fructose, it ties up the anomeric carbons of both glucose and fructose.
 This linkage gives sucrose certain properties that are quite different
from those of maltose and lactose. As long as the sucrose molecule
remains intact, neither monosaccharide “uncyclizes” to form an open-
chain structure. Thus, sucrose is incapable of mutarotation and exists in
only one form both in the solid state and in solution. In addition,
sucrose does not undergo reactions that are typical of aldehydes and
ketones. Therefore, sucrose is a nonreducing sugar.
 The hydrolysis of sucrose in dilute acid or through the action of the
enzyme sucrase (also known as invertase) gives an equimolar mixture
of glucose and fructose. This 1:1 mixture is referred to as invert sugar
because it rotates plane-polarized light in the opposite direction than
sucrose. The widespread use of sucrose is a contributing factor to
obesity and tooth decay. Carbohydrates such as sucrose, are converted
to fat when the caloric intake exceeds the body’s requirements, and
sucrose causes tooth decay by promoting the formation of plaque that
https://chem.libretexts.org/Courses/Sacramento_City_College/SCC%3A_Chem_309_-
sticks to teeth. _General_Organic_and_Biochemistry_(Bennett)/Text/14%3A_Carbohydrates/14.6%3A_
http://www.chups.jussieu.fr/polys/biochimie/SGLbioch/POLY.Chp.1.5.htm Disaccharides
l
 Polysaccharides

 Polysaccharides (glycans), are long chain polymeric

carbohydrates composed of monosaccharide units ( more than
20) bound together by glycosidic linkages. This carbohydrate
can react with water (hydrolysis) using enzymes as catalyst,
which produces constituent sugars (monosaccharides, or
oligosaccharides). They range in structure from linear to highly
branched. Examples include storage polysaccharides such as
starch, glycogenand structural polysaccharides such as cellulose.
 Polysaccharides can be broadly classified into two
classes:
 Homo-polysaccharides – are made up of one type of
monosaccharide units. ex: cellulose, starch, glycogen.
 Hetero-polysaccharides – are made up of two or
more types of monosaccharide units. ex. hyaluronic
acid and they provide extracellular support
for organisms.

https://www.slideshare.net/ArunimaSur/classification-of-polysaccharides-gluconeogenesis-and-
glucogenolysis
 Glycogen
 Glycogen is a branched biopolymer consisting of linear chains of glucose
residues with an average chain length of approximately 8–12 glucose units
and 2,000-60,000 residues per one molecule of glycogen. Glycogen has a
structure similar to amylopectin (a component of starch), but is more
extensively branched and compact than starch.
 Glucose units are linked together linearly by α(1→4) glycosidic bonds from
one glucose to the next. Branches are linked to the chains from which they
are branching off by α(1→6) glycosidic bonds between the first glucose of
the new branch and a glucose on the stem chain. Each glycogen
molecule has a protein, glycogenin, covalently linked to
the polysaccharide.
 Glucose is an osmotic molecule, and can have profound effects on osmotic
pressure in high concentrations possibly leading to cell damage or death if
stored in the cell without being modified. Glycogen is a non-osmotic
molecule, so it can be used as a storing glucose in the cell without
disrupting osmotic pressure.
 The branched structure of glycogen allows you to quickly regulate glucose
levels by attaching new glucose residues to the ends of the molecule during
hyperglycemia or rapidly cleaving off glucose residues during
hypoglycemia.
 In the liver, glycogen regulates blood glucose level as it breaks down to free
glucose that is released from the cell. Liver glycogen stores are enough for
https://www.sciencedirect.com/topics/neuroscience/glycogen
about 12-18 hours of fasting. In other cells, especially in skeletal muscle,
glycogen is broken down to glucose-6-phosphate, which does not leave the
cell, but is actively oxidized to produce energy that is used by the cell.
 Starch

 Starch is the most important source of glucose in the human diet and
accounts for more than 50% of our carbohydrate intake. It occurs in plants
in the form of granules, and these are particularly abundant in seeds
(especially the cereal grains) and tubers, where they serve as a storage form
of carbohydrates. Plants contain a percentage of starch (potatoes 15%,
wheat 55%, corn 65%, and rice 75%).
 Starch is a mixture of two polymers: amylose and amylopectin. Natural
starches consist of about 10%–30% amylose and 70%–90% amylopectin.
 Amylose is a linear polysaccharide composed entirely of D-glucose units
joined by the α-1,4-glycosidic bonds. Amylose is not a straight chain of
glucose units but instead is coiled like a spring, with six glucose monomers
per turn. When coiled in this fashion, amylose has just enough room in its
core to accommodate an iodine molecule. The characteristic blue-violet
color that appears when starch is treated with iodine is due to the formation
of the amylose-iodine complex. This color test is sensitive enough to detect
even minute amounts of starch in solution.
 Amylopectin is a branched-chain polysaccharide composed of glucose
units linked primarily by α-1,4-glycosidic bonds but with α-1,6-glycosidic
bonds, which are responsible for the branching. A molecule of amylopectin
may contain many thousands of glucose units with branch points occurring
about every 25–30 units. The helical structure of amylopectin is disrupted
by the branching of the chain, so instead of the deep blue-violet color
amylose gives with iodine, amylopectin produces a less intense reddishhttps://www.easybiologyclass.com/polysaccharides-structure-classification-and-examples-biochemistry-
brown. lecture-notes/
 Cellulose

 Cellulose is a polysaccharide consisting of a linear chain of

several hundred to many thousands of β(1→4) linked β-D-
glucose units.
 Cellulose, a fibrous carbohydrate found in all plants, is the
structural component of plant cell walls.
 Like amylose, cellulose is a linear polymer of glucose. It differs,
however, in that the glucose units are joined by β-1,4-glycosidic
linkages, producing a more extended structure than amylose.
This extreme linearity allows a great deal of hydrogen bonding
between OH groups on adjacent chains, causing them to pack
closely into fibers. As a result, cellulose exhibits little interaction
with water or any other solvent. Because cellulose does not have
a helical structure, it does not bind to iodine to form a colored
product.
 People cannot digest cellulose, but it is as important in the diet as
fiber. Fiber improves intestinal motility, gives a feeling of satiety
and promotes the formation of feces and accelerates its excretion
from the body. In addition, the cage helps to remove toxic
substances from the body.

https://www.easybiologyclass.com/polysaccharides-structure-classification-and-examples-
biochemistry-lecture-notes/
 Heteropolysaccharides.

 In general, heteropolysaccharides (heteroglycans) contain two or more different monosaccharide units. Although a few representatives
contain three or more different monosaccharides, most naturally occurring heteroglycans contain only two different ones and are closely
associated with lipid or protein. The major heteropolysaccharides include the connective-tissue polysaccharides, the blood group
substances, glycoproteins (combinations of carbohydrates and proteins) such as gamma globulin, and glycolipids (combinations of
carbohydrates and lipids), particularly those found in the central nervous system.

heteropolysaccharide component sugars functions distribution

D-glucuronic acid and N- lubricant, shock absorber,

hyaluronic acid connective tissue, skin
acetyl-D-glucosamine water binding

D-glucuronic acid and N- calcium accumulation,

chondroitin-4-sulfate acetyl-D-galactosamine-4- cartilage and bone cartilage
O-sulfate formation

D-glucuronic acid, L-
heparin iduronic acid, N-sulfo-D- anticoagulant mast cells, blood
glucosamine

N-acetyl-hexosamine, D-
gamma globulin antibody blood
mannose, D-galactose

D-glucosamine, D-
cell surfaces, especially
blood group substance galactosamine, L-fucose, blood group specificity
red blood cells
D-galactose
 Glycosaminoglycans

 Glycosaminoglycans (GAGs) or mucopolysaccharides

are long linear polysaccharides consisting of repeating
disaccharide units (i.e. two-sugar units). The repeating
two-sugar unit consists of a uronic sugar (glucuronic
or iduronic acid) and an amino sugar (glucosamine or
galactosamine), with the exception of keratan, where in
the place of the uronic sugar it has galactose. Because
GAGs are highly polar and attract water, they are used in
the body as a lubricant or shock absorber.

 Mucopolysaccharidoses are a group of metabolic

disorders in which abnormal accumulations of
glycosaminoglycans occur because of enzyme
deficiencies.

https://www.researchgate.net/figure/Structure-of-the-different-glycosaminoglycan-
chains_fig2_12681530
 Glycosaminoglycans

Hyaluronic acid
 Hyaluronic acid (HA) is ubiquitous in body tissues and
is best-known for its capability of attracting water
molecules. The highly polar structure of HA makes it
capable of binding 10000 times its own weight in water.
Due to this characteristic, it plays a key role in
lubrication of synovial joints and wound healing
processes.
 Hyaluronic acid binds cells together, lubricates joints,
and helps maintain the shape of the eyeballs. The
viscoelasticity of hyaluronic acid make it ideal for
lubricating joints and surfaces that move along each
other, such as cartilage.
 Hyaluronic acid regulates transport of substances
between cells. For example, hyaluronan helps partition
plasma proteins between vascular and extravascular
spaces, which affects solubility of macromolecules in
the interstitium, changes chemical equilibria, and https://www.researchgate.net/figure/Fig-1-Structure-of-Hyaluronic-acid-molecule-HA_fig1_23656785

stabilizes the structure of collagen fibers.

 Heparin Keratan-, dermatan sulfates

 Heparin is an anticoagulant activator of antitrombin  Keratan sulfates (KS), is the maintenance of tissue
III. Endogenous heparin is localized and is protonated hydration. Keratan sulfates are in the bone, cartilage, and
the cornea of the eye. Within the normal cornea, dermatan
(H2A2+) at pH wistored in secretory granules of mast sulfate is fully hydrated whereas keratan sulfate is only
cells. Histamine that is present within the granules thin partially hydrated suggesting that keratan sulfate may
granules (5.2–6.0), thus it is believed that heparin, behave as a dynamically controlled buffer for hydration.
which is highly negatively charged, functions to
 Keratan sulfate GAGs are found in many other tissues
electrostatically retain and store histamine. Heparan besides the cornea, where they are known to regulate
sulfate (HS) has regulates of cell adhesion, regulats of macrophage adhesion, form barriers to neurite growth,
cell growth and proliferation, developmental processes, regulate embryo implantation in the endometrial uterine
cell surface binding of lipoprotein lipase and other lining during menstrual cycles, and affect the motility of
proteins, angiogenesis, viral invasion, and tumor corneal endothelial cells. In summary, KS plays an anti-
adhesive role, which suggests very important functions of
metastasis. KS in cell motility and attachment.
 Dermatan sulfates function in the skin, tendons, blood
vessels, and heart valves.
 Proteoglycans

 Proteoglycans are proteins that consists of a "core protein" with one or

more covalently attached glycosaminoglycan (GAG) chain(s). The
chains are long, linear carbohydrate polymers that are negatively
charged under physiological conditions due to the occurrence of sulfate
and uronic acid groups. Proteoglycans occur in connective tissue.
 Proteoglycans (PG) are a major component of the extracellular matrix
of connective tissue, the "filler" substance existing between cells in an
organism. They form large complexes, both to other proteoglycans, to
hyaluronan, and to fibrous matrix proteins, such as collagen.
 The combination of proteoglycans and collagen form cartilage, a sturdy
tissue that is usually heavily hydrated (mostly due to the negatively
charged sulfates in the glycosaminoglycan chains of the proteoglycans).
 PG are involved in binding cations (such as sodium, potassium and
calcium) and water, and also regulating the movement of molecules
through the matrix.
 PG can affect the activity and stability of proteins and signalling
molecules within the matrix.
 PG can serve as lubricants, by creating a hydrating gel that helps
withstand high pressure. https://pediaa.com/difference-between-proteoglycan-and-
glycoprotein/
 Sources of information

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 https://www.slideshare.net/ArunimaSur/classification-of-polysaccharides-gluconeogenesis-and-
glucogenolysis
 https://www.sciencedirect.com/topics/neuroscience/glycogen
 https://www.easybiologyclass.com/polysaccharides-structure-classification-and-examples-
biochemistry-lecture-notes/#starch-structure
 https://www.easybiologyclass.com/polysaccharides-structure-classification-and-examples-biochemistry-lecture-
notes/
 https://www.researchgate.net/figure/Structure-of-the-different-glycosaminoglycan-
chains_fig2_12681530
 https://www.researchgate.net/figure/Fig-1-Structure-of-Hyaluronic-acid-molecule-HA_fig1_23656785
 https://pediaa.com/difference-between-proteoglycan-and-glycoprotein/
Biological and Bioorganic Chemistry. In 2 books. Book 1. Bioorganic Chemistry.
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