Cebu Doctors’ University – College of Arts and Sciences

MC2– Biochemistry

Lecture Notes on
CHEMISTRY OF CARBOHYDRATES
Prepared by: Joselito R. Tumulak Jr.
Biochemistry Instructor

I. OVERVIEW
- Carbohydrates are the most abundant biomolecule in nature, since they are produced massively by photosynthetic organisms.
Energy from the sun captured by green plants, algae, and some bacteria during photosynthesis converts more than 250 billion kilograms
of carbon dioxide into carbohydrates every day on earth.
- They are chemically simpler than nucleic acids and proteins, containing just three elements – carbon, hydrogen, and oxygen.

Functions of Carbohydrates
1. Carbohydrates are metabolic precursors of virtually all other biomolecules since they are the main products of the producers,.
2. Breakdown of carbohydrates provides the energy (4 kcal/g) that sustains animal life.
3. Carbohydrates are covalently linked with a variety of other molecules. These are known as glycoconjugates, and are important
components of cell walls and extracellular structures in plants, animals, and bacteria.
4. Carbohydrates also serve in a variety of processes involving recognition between cell types or recognition of cellular
structures by other molecules. Recognition events are important in normal cell growth, fertilization, transformation of cells,
and other processes.

Chemical Features of Carbohydrates

- All of the functions mentioned above are made possible by the characteristic chemical features of carbohydrates:
 the existence of at least one and often two or more stereogenic carbons
 the ability to exist either in linear or ring structures
 the capacity to form polymeric structures via glycosidic bonds
 the potential to form multiple hydrogen bonds with water or other molecules in their environment.

Structural Definition of Carbohydrates

- Historically, carbohydrates are so called because the earliest known carbohydrates contain carbon as well as hydrogen and oxygen
in the ratio of 2:1 just like water. They follow the general formula Cn(H2O)m. For example, the formula for glucose is C6H12O6 which can
also be written as C6(H2O)6.
- As more carbohydrates are discovered, it was found out that some carbohydrates do not follow the general formula. For example,
deoxyribose (a carbohydrate found in DNA) has a formula of C5H10O4. It did not fit the general formula of a hydrate of carbon, yet it is a
carbohydrate. Also, such compounds such as acetic acid, CH 3COOH may fit the general formula since it can be written as C2(H2O)2, but
is not a carbohydrate.
- To correctly define carbohydrates, we need to have a structural definition. Structurally, carbohydrates are known as polyhydroxy
aldehydes and ketones or substances that yields these compounds upon hydrolysis.

- Example:
O
aldehyde
II
CH2OH
C–H
I
I ketone C=O
H – C – OH
I
I
HO – C – H
HO – C – H polyhydroxy I
I - with a lot of -OH
H – C – OH
H – C – OH
I
I
H – C – OH
H – C – OH
I
I
CH2OH
CH2OH
D- glucose D-fructose
Classification of Carbohydrates
- Carbohydrates are classified according to the number of saccharide (sugar) units. The term saccharide is derived from the Latin word
“saccharum” which means “sweet”.
- Carbohydrates are classified into:
1. Monosaccharides – contains one saccharide unit; simplest sugar unit
Example:
glucose (blood sugar)
fructose (fruit sugar)
galactose

2. Disaccharides – contains two monosaccharide units

Example:
sucrose (table sugar) = glucose + fructose
lactose (milk sugar) = glucose + galactose
maltose (malt sugar) = glucose + glucose

3. Polysaccharides – made up of polymers or chains of monosaccharide units

Example:
starch = polymer of glucose
glycogen = polymer of glucose
inulin = polymer of fructose

Comparison of Physical Properties:

Property Monosaccharide Disaccharide Polysaccharide
Appearance Crystalline crystalline amorphous, powdery
Taste Sweet sweet tasteless
Solubility in water Soluble soluble slightly soluble ; insoluble
*The term sugar refers to monosaccharides and disaccharides only since both types of carbohydrates generally have a sweet
taste. Polysaccharides are also referred to as glycans.

II. MONOSACCHARIDES
- Monosaccharides are the smallest unit of sugars which cannot be further hydrolyzed.
- They typically contain 3-6 carbon atoms, and has at least one stereogenic carbon, except for dihydroxyacetone.

Classification of Monosaccharides
- There are 2 ways to classify monosaccharides:
1. According to the number of carbon atoms
 Triose – contains 3 C atoms
 Tetrose - contains 4 C atoms
 Pentose - contains 5 C atoms
 Hexose - contains 6 C atoms

2. According to the type of carbonyl group present

 Aldoses – monosaccharides that contain CHO (aldehyde) at Carbon 1.
 Ketoses – monosaccharides that contain C=O (ketone) at Carbon 2.
- Example:

O aldehyde (@C1)
II aldose
CH2OH
C–H
I
I ketone (@C2)
ketose C=O
H – C – OH
I
I
HO – C – H
HO – C – H
6 carbon atoms I
I
- both are hexoses H – C – OH
H – C – OH
I
I
H – C – OH
H – C – OH
I
I
CH2OH
CH2OH
D- glucose D-fructose

- We can combine the classification of 2 sugars above by saying D-glucose is an aldohexose, and D-fructose is a ketohexose.
Structure of the Monosaccharides

Aldoses

Ketoses

Isomerism in Monosaccharides
- Isomers are molecules having the same molecular formula, that is they contain the same elements present and the same number
of atoms for each element. However, their arrangement, connectivity and orientation in space may be different thus, resulting to
different molecules.
- Types of Monosaccharide Isomers:
1. Constitutional Isomers – the same molecular formula but functional groups and different order of the bonding atoms
- Example:

O aldehyde (@C1)
II
CH2OH
C–H
I
I
C=O
H – C – OH ketone (@C2)
I
I
HO – C – H
HO – C – H
both have the I
I
molecular formula of H – C – OH
H – C – OH
C6H12O6 I
I
H – C – OH
H – C – OH
I
I
CH2OH
CH2OH
D-glucose D-fructose
- Both sugars have the same molecular formula, C6H12O6. However, since they have different functional groups, and the atoms are
bonded differently, D-glucose and D-fructose are constitutional isomers.

2. Stereoisomers - isomers that have the same molecular formula and functional group, but differ in the orientation of atoms around the
molecule.
- Example:
O O
Both have
II II
aldehyde
C–H C–H
I I
H – C – OH differ only HO – C – H
I at the arrange- I
C5H10O5 H – C – OH ments of these HO – C –H C5H10O5
I atoms I
H – C – OH H – C – OH
I I
CH2OH CH2OH

D-ribose D-lyxose
- Both sugars have the same molecular formula, C 6H12O6 and the same functional groups, but differ only in the arrangement of –OH in a
carbon. Thus, D-ribose and D-lyxose are stereoisomers.

Stereogenic Carbon
- The difference in the orientation of atoms are usually in their stereogenic (chiral) carbons. Recall, that monosaccharides have often
at least 1 and often 2 or more stereogenic carbon, except dihydroxyacetone.
- A stereogenic carbon is a saturated carbon with four different groups around it.
O
II
C–H
I
H – C – OH
I stereogenic carbon
CH2OH
D-glyceraldehyde

CH2OH
I
C=O
I
CH2OH
Dihydroxyacetone

- A compound containing stereogenic carbon is a considered a chiral compound and is capable of stereoisomerism.
Dihydroxyacetone has no stereogenic carbon, and is therefore, achiral.
- Types of Stereoisomers:
1. Enantiomers - stereoisomers whose molecules are non-superimposable mirror images of each other. They can be designated:
- D – the –OH of the penultimate carbon is directed to the right.
- L – the –OH of the penultimate carbon is directed to the left.
- Example:
O O
II II
C–H C–H
I I
H – C – OH HO – C –H
I I
HO – C – H H – C – OH
I I
H – C – OH HO – C –H
I I
H – C – OH HO – C –H
I I
CH2OH CH2OH
D-glucose L-glucose
 Are they stereoisomers?
- Both molecules have the same functional groups and the same order of connectivity of the atoms. They differ only in the
orientation of the H and OH groups. Thus, the two molecules are stereoisomers.
 What type of stereoisomers are they?
- The two molecules are mirror images of each other wherein the H and OH groups are interchanged in the stereogenic carbons of
both molecules. The mirror images are nonsuperimposable since if the two molecules will be overlapped, the H and OH groups
will not coincide. Thus, the molecules are enantiomers.
- To distinguish the enantiomers from each other, the glucose whose OH of its penultimate carbon is at the right, is named as D-
glucose. The glucose whose OH of its penultimate carbon is at the left is named as L-glucose.

2. Diastereomers – stereoisomers which are not mirror images of each other.

- Example: O O
II II
C–H C–H
I I
H – C – OH HO – C – H
I I
HO – C – H H – C – OH
I I
H – C – OH H – C – OH
I I
H – C – OH H – C – OH
I I
CH2OH CH2OH

D-glucose D-altrose
 Are they stereoisomers?
- Both molecules have the same functional groups and the same order of connectivity of the atoms. They differ only in the
orientation of the H and OH groups. Thus, the two molecules are stereoisomers.
 Are they diastereomers?
- The two sugars are not mirror images of each other since not all the H and OH groups are interchanged. Thus, the sugars are
diastereomers.

3. Epimers – special class of diastereomers that differ in the position of only one –OH group.
- Example: O
O
II II
C–H C–H
I I
H – C – OH HO – C –H
I I
D-ribose H – C – OH H – C – OH D-arabinose
I I
H – C – OH H – C – OH
I I
CH2OH CH 2OH
  Are they stereoisomers?
- Both molecules have the same functional groups and the same order of connectivity of the atoms. They differ only in the
orientation of the H and OH groups. Thus, the two molecules are stereoisomers.
 Are they diastereomers?
- The two sugars are not mirror images of each other since not all the H and OH groups are interchanged. They inly differ at one
carbon, carbon number 2, thus the sugars are epimers. We could say that D-ribose is the C2 epimer of D-arabinose. Meaning, D-
ribose only differ from D-arabinose at carbon 2.

- In order for you to easily determine the isomerism present in 2 sugars, follow this thinking pattern below:

Do the 2 monosaccharides have the same molecular formula?

Yes. No.
They are isomers. They are not
isomers.

Do they have the same carbonyl group?

Yes.
No.

They are stereoisomers.

They are constitutional
isomers.

Are they mirror images?

No.
Yes.

They are diastereomers.

They are
enantiomers.

Do they differ only at one carbon?

Yes.

They are epimers.

No.

They are
diastereomers.
Fischer Projection of Monosaccharides
- Notice how the structures of the monosaccharides are illustrated above. This way of drawing the structure of monosaccharides are
known as the Fischer Projection. It is a 2-D representation of the arrangement of groups around stereogenic carbons which represents
the open-chain conformation of the monosaccharide.
- Using this projection, the monosaccharide is drawn vertically, where the carbonyl group is at or near the top. Counting of carbon
always begin at the top.

O
II
C–H 1 CH2OH
I I
H – C – OH 2 C=O
I I
HO – C – H 3 HO – C – H
I I
H – C – OH 4 H – C – OH
I I
5 H – C – OH
H – C – OH
I I
6
CH2OH CH2OH
D-glucose D-fructose

Cyclic Structure of Monosaccharides

- Alcohols react with carbonyl of aldehydes and ketones to form hemiacetals and hemiketals, respectively.

- Likewise, the hydroxyl and either aldehyde or ketone groups of monosaccharides can react intramolecularly to form cyclic
hemiacetals and hemiketals.
- The British carbohydrate chemist Sir Norman Haworth showed that the linear form of glucose (and other aldohexoses) could undergo
said intramolecular reaction to form a cyclic hemiacetal (See Figure below). In the reaction, the aldehyde group of glucose reacts with
its penultimate hydroxyl group. The result is a six-membered, oxygen-containing ring which is similar to pyran and is designated a
pyranose. The reaction is catalyzed by acid (H+) or base (OH-) and is readily reversible.

- The analogous intramolecular reaction of a ketose sugar such as fructose yields a cyclic hemiketal (See Figure below). In the reaction,
the ketone group of fructose reacts with its penultimate hydroxyl group. The result is a five-membered, oxygen-containing ring,
which is reminiscent of furan and is referred to as a furanose. Aldopentoses also form furanoses.
- The cyclic pyranose and furanose forms are the preferred structures for monosaccharides in aqueous solution. At equilibrium, the
linear aldehyde or ketone structure is only a minor component of the mixture (generally much less than 1%).

Anomers
- When hemiacetals and hemiketals are formed, notice how the carbonyl carbons of the linear structures become stereogenic carbon
atoms. Isomers of monosaccharides that differ only in the configuration about that carbon atom are called anomers, designated as α or
β, as shown in previous figures. The carbonyl carbon is thus called the anomeric carbon.
 How to distinguish α anomer from β anomer based on structural representation?
- An α anomer has the –OH of the anomeric carbon in opposite direction as the terminal –CH2OH.
- A β anomer has the –OH of the anomeric carbon in similar direction as the terminal –CH2OH.

α anomer β anomer

- In an aqueous solution of monosaccharides, a dynamic equilibrium exists among the α, β, and open-chain forms, which means that
there is a continual interconversion among them. For example, a freshly mixed solution of pure D-glucose slowly converts to a mixture
of both α- and β anomers of glucose by an opening and a closing of the cyclic structure. When equilibrium is established, 63% of the
molecules in the solutions are in the β form, 37% are in the α form, and less than 0.01% are in the open chain form.

37% >0.01% 63%

Nomenclature of Cyclic Monosaccharides

- When a monosaccharide cyclizes, it assumes a different name. It follows the format:
type of anomer (α or β) – type of enantiomer (D or L) – name of monosaccharide removed with –se + type of ring

- Example:

- This a cyclic structure of D-glucose.

- This is a β anomer of glucose since the–OH of the anomeric carbon is similar of direction to the
terminal –CH2OH.
- The name is β-D-glucopyranose.
Haworth Projection of Monosaccharides
- Notice how the pyranoses and furanoses were illustrated in the previous pages. This way of representing the cyclic structure of
monosaccharides is known as the Haworth projection, which is another of Sir Haworth’s lasting contribution to the field of carbohydrate
chemistry.
- In the Haworth projection, pyranoses are represented as hexagonal rings lying perpendicular to the plane of the paper, with
thickened line indicating the side of the ring closest to the reader. The acetal oxygen is located on the upper right corner of the hexagon,
and the anomeric carbon (carbon 1) is the rightmost vertex. Counting of carbon goes in a clockwise direction.
- Furanoses are represented as pentagonal rings lying perpendicular to the plane of the paper, with thickened line indicating the side
of the ring closest to the reader. The acetal oxygen is located on the upper corner of the pentagon, and the anomeric carbon (carbon
1 if aldopentose and carbon 2 if ketohexose) is the rightmost vertex. Counting of carbon goes also in a clockwise direction.

Position of the Hydroxyl (-OH) groups in Haworth Projection

- In a Haworth projection, the terminal –CH2OH determines whether the monosaccharide is D or L. For D monosaccharides, the
terminal –CH2OH is directed upwards. For L monosaccharides, the terminal –CH2OH is directed downward.
- All –OH directed to the right side in the Fischer projection are drawn directed downwards in a Haworth projection. All –OH
directed to the left side in a Fischer projection of monosaccharides are drawn directed upwards in a Haworth projection.
- And as mentioned earlier, α anomer has the –OH of the anomeric carbon in opposite direction as the terminal –CH2OH. A β
anomer has the –OH of the anomeric carbon in similar direction as the terminal –CH2OH.

Converting Fischer Projection to Haworth Projection

- Example:
1. Convert the Fischer projection of D-glucose below into its Haworth projection in α anomer.
O
II
C–H
I
H – C – OH
I
HO – C – H
I
H – C – OH
I
H – C – OH
I
CH2OH
Solution:
a. D-glucose is an aldohexose, thus the ring that it will have is a pyranose. The anomeric carbon is at carbon 1 because the
carbonyl of D-glucose is at carbon 1.

C5
O

C4 C1 anomeric carbon
C3 C2

b. Since the type of enantiomerism is D, the terminal -CH2OH should be directed upwards attached to C5.

CH2OH

c. Since the type of anomer is α, the –OH of the anomeric carbon (C1) should be directed in opposite direction as the terminal –
CH2OH, that is downwards.
CH2OH

OH
d. The –OH of carbons 2 and 4 are directed to the right of the Fischer projection of D-glucose, so both of them should be directed
downwards in the Haworth Projection. The –OH of carbon 3 is directed to the left of the Fischer projection of D-glucose, so it
should be directed upwards in the Haworth Projection.
 CH2OH

OH

OH OH

OH
e. To name the cyclic structure, start with the anomer, followed by the enantiomer, and then name of the monosaccharide removed
with –se and added with the type of ring as suffix. Thus,
 Name: α-D-glucopyranose

2. Convert the Fischer projection of D-fructose below into its Haworth projection in β anomer.
CH2OH
I
C=O
I
HO – C – H
I
H – C – OH
I
H – C – OH
I
CH2OH
Solution:
a. D-fructose is a ketohexose, thus the ring that it will have is a furanose. The anomeric carbon will be at carbon 2 since the
carbonyl in fructose is at carbon 2.

C5 C2 anomeric carbon

C4 C3

b. Since the type of enantiomerism is D, the terminal -CH2OH should be directed upwards attached to C5.

CH2OH O

c. Since the type of anomer is β, the –OH of the anomeric carbon should be directed in the same direction as the terminal –CH2OH,
that is upwards. Also, the –CH2OH at the beginning (C1) would then be place downwards.

CH2OH O OH

CH2OH

d. The –OH of carbon 3 is directed to the left of the Fischer projection of D-fructose, so it should be directed upwards in the Haworth
Projection. The –OH of carbon 4 is directed to the right of the Fischer projection of D-fructose, so it should be directed downwards
in the Haworth Projection.

CH2OH O OH

OH CH2OH

OH
e. To name the cyclic structure, start with the anomer, followed by the enantiomer, and then name of the monosaccharide removed
with –se and added with the type of ring as suffix. Thus,
 Name: β-D-fructofuranose
3. Convert the Fischer projection of D-ribose below into its Haworth projection in α anomer.
O
II
C–H
I
H – C – OH
I
H – C – OH
I
H – C – OH
I
CH2OH
Solution:
a. D-ribose is a aldopentose, thus the ring that it will have is a furanose. The anomeric carbon will be at carbon 1 since the carbonyl
in fructose is at carbon 1.

C4 C1 anomeric carbon

C3 C2

b. Since the type of enantiomerism is D, the terminal -CH2OH should be directed upwards attached to C4.

CH2OH O

c. Since the type of anomer is α, the –OH of the anomeric carbon should be directed in opposite direction as the terminal –CH2OH,
that is downwards.

CH2OH O

OH

d. The –OH of carbons 2 and 3 are directed to the right of the Fischer projection of D-ribose, so they should be directed downwards
in the Haworth Projection.

CH2OH O

OH

OH OH

e. To name the cyclic structure, start with the anomer, followed by the enantiomer, and then name of the monosaccharide removed
with –se and added with the type of ring as suffix. Thus,
 Name: α-D-ribofuranose

Monosaccharides of Physiologic Importance

Sugar Where Found Biochemical Importance
D-ribose Nucleic acids Structural elements of nucleic acids and co
enzymes, e.g. ATP, NAD, NADP, and flavoproteins;
Ribose phosphates are intermediate of pentose
phosphate pathway
D-ribulose Formed in metabolic processes Ribulose phosphates are intermediate of pentose
phosphate pathway
D-arabinose Gum Arabic, plum and cherry gums Constituent of glycoproteins
D-xylose Wood gums, proteoglycans, Constituent of glycoproteins
glycosoaminoglycans
 D-lyxose Heart muscle A constituent of lyxoflavin isolated from human heart
muscle
L-xylulose Intermediate in uronic pathway
D-glucose (dextrose) Fruit juices, hydrolysis of starch, cane The “sugar” of the body; This is carried by the blood,
sugar, maltose and lactose and principally used by the tissues.
D-fructose (levulose) Fruit juices, honey, hydrolysis of cane Can be changed into glucose in the liver and so is
sugar and inulin used in the body; sweetest sugar
D-galactose Hydrolysis of lactose Can be changed into glucose in the liver and so is
used in the body; synthesized in the mammary gland
to make lactose (milk sugar); a constituent of
glycolipid and glycoproteins.
D-mannose Hydrolysis of plant mannans and gums Constituent of many glycoproteins

Monosaccharide Derivatives
1. Sugar Acids
- Recall the oxidation reaction of primary alcohols and aldehydes:

Oxidation Oxidation

Primary Alcohol Aldehyde Carboxylic Acids

-CH2OH O O
II II
–C–H – C – OH

Oxidation
- Aldoses may undergo oxidation since they have aldehyde group and primary alcohol group. These are the 2 possible sites for oxidation
in an aldose:
O
II
C–H aldehyde
I
H – C – OH
I
HO – C – H
I site of oxidation
H – C – OH
I
H – C – OH
I
CH2OH primary
alcohol
- Oxidation of aldoses yields 3 different sugar acids:
1. Aldonic acid
2. Aldaric acid
3. Alduronic acid (Uronic acid)
- The type of sugar acid produced is dependent on the type of oxidizing agent involved in the reaction.

a. Aldonic Acid
- When open-chain aldoses are reacted with weak oxidizing agents (e.g. Fehling’s reagent, Benedict’s reagent, and Tollen’s
reagent), their aldehydes are converted to carboxylic acids. This result to formation of aldonic acids. The weak oxidizing agents
are often metal ion solution in basic condition (pH above 7).
 - Example:
O O
II II
C–H C – OH
I I
H – C – OH
Benedict’s H – C – OH
I (Cu2+) I
HO – C – H HO – C – H
I I
H – C – OH H – C – OH
I I
H – C – OH H – C – OH
I I
CH2OH CH2OH
D-Glucose D-Gluconic acid
- The aldonic acid that is produced is named by replacing the suffix –ose in the original name of aldose with the suffix -onic
acid.
- The weak oxidizing agents used are often colored solutions which will change in color after the reaction due to the
formation of a colored reduced product. Listed below are some of these weak oxidizing agents and their respective colored
reduced product.
Reagent Oxidizing Agent Original Color Reduced Product Positive Result
Blue brick red precipitate

Benedict’s Reagent Cu2+ Cu2O

Blue brick red precipitate

Fehling’s Reagent Cu2+ Cu2O

Colorless silver mirror

Tollen’s Reagent Ag+ Ag

Colorless black precipitate

Nylander’s Reagent Bi3+ Bi

yellow mahogany red solution

Picric Acid test picric acid picramic acid

 - Carbohydrates that can reduce these weak oxidizing agents are known as reducing sugars.
- Ketoses are also reducing sugars.
 By principle, ketoses do not have reducing property like aldoses because they do not contain an aldehyde group.
 However, in the laboratory, ketoses will give a positive result to the test for reducing sugars.
 The reason for this is that at basic condition, ketoses tautomerize into mixture of aldoses. Since weak oxidizing agents
are basic, they are able to convert ketoses to aldoses, and then the newly formed aldoses will then undergo oxidation.
- Benedict’s test can be used to test for glucose in urine, a condition known as glucosuria and a symptom for diabetes. The
glucose content of urine can be determined by dipping a plastic strip treated with Benedict’s solution and comparing the color
change of the strip to a color chart that indicates glucose concentration. The disadvantage of this test is that it may also give a
positive result to other reducing sugars that may be present in the sample.

- A more recent method for the detection of glucose is the used of glucose oxidase, an enzyme highly specific for glucose. In
this case, it removes the disadvantage of false positive.

b. Aldaric Acid
- When aldoses are reacted with strong oxidizing agents (e.g. hot concentrated nitric acid (HNO3)), their aldehydes and primary
alcohols are both converted to carboxylic acids. This result to formation of aldaric acids.
- Example:
O O
II II
C–H C – OH
I I
H – C – OH
Hot conc. H – C – OH
I HNO3 I
HO – C – H HO – C – H
I I
HO – C – H HO – C – H
I I
H – C – OH H – C – OH
I I
CH2OH C – OH
II
O

D-Galactose D-Galactaric acid

- The aldaric acid that is produced is named by replacing the suffix –ose in the original name of aldose with the suffix -aric
acid.
- Galactaric acid (mucic acid) is the only aldaric acid that is insoluble in cold water. Thus, conversion of galactose to mucic
acid using hot concentrated HNO3 can be used to identify galactose.

c. Alduronic acid (Uronic acid)

- Monosaccharides can undergo enzymatic oxidation at their primary alcohols converting them to carboxylic acids. This produces
alduronic acids or simply uronic acids.
- Example:
O
O
II
II
C–H
C–H
I
I
H – C – OH
H – C – OH
I
Enzymes I
HO – C – H
HO – C – H
I
I
H – C – OH
H – C – OH
I
I
H – C – OH
H – C – OH
I
I
C – OH
CH2OH
II
O
D-Glucose D-Glucuronic acid
 - The alduronic acid that is produced is named by replacing the suffix –ose in the original name of aldose with the suffix -
uronic acid (e.g. galactose-galacturonic acid).
- Alduronic acids may also exist as cyclic structures, since the aldehyde group can still react intramolecularly with the hydroxyl
group of the penultimate carbon.
CHO
I
COOH
H – C – OH
I O
HO – C – H
I OH
H – C – OH
OH OH
I
H – C – OH OH
I
COOH

- Uronic acids like α–D–glucuronic acid is used by the body to detoxify foreign phenols and alcohols; in the liver, these
compounds are converted to glycosides of glucuronic acid and excreted in the urine.
- α-D-Glucuronic acid is widely distributed in the plant and animal world. In humans, it is an important component of the acidic
polysaccharides of connective tissues.
- When the H+ of the carboxyl group of an alduronic acid is removed, it becomes it conjugate base, alduronate. Meaning to
say, glucoronate is the conjugate base of glucuronic acid.

2. Sugar Alcohols (Alditols)

- Reduction converts the aldehyde of an aldose or the ketone of a ketose into a primary alcohol and a secondary alcohol,
respectively.
- The reducing agents that can be used include NaBH4; and H2 in the presence of a transition metal catalyst like Palladium (Pd) or
Platinum (Pt).
- Example:
CHO
CH2OH
I
I
H – C – OH
H – C – OH
I
I
HO – C – H NaBH4 HO – C – H
I
I
H – C – OH
H – C – OH
I
I
H – C – OH
H – C – OH
I
I
CH2OH
CH2OH

D-Glucose D-Glucitol (Sorbitol)

- The alditol that is produced is named by replacing the suffix –ose in the original name of aldose with the suffix –itol.
- Common alditols and their functions:
1. Xylitol – component of sugar free gum
2. Glucitol or sorbitol is found in the plant world in many berries and in cherries, plums, pears, apples, seaweed, and algae. It is
also used as a sweetening agent. Accumulation of sorbitol in the eye is a major factor in the formation of cataracts.
3. Mannitol is now used in the treatment of malignant brain tumors. It is injected directly into the brain’s main arteries to lower the
blood-brain barrier and allow chemotherapeutic agents to be administered intravenously.
- Alditols are used as moisturizing agents in food and in cosmetic products.

3. Amino Sugars
- If one of the hydroxyl groups of a monosaccharide is replaced with an amino group (NH2), an amino sugar is produced.
- Example:
CH2OH CH2OH

O O

OH OH
OH OH OH OH
OH NH2
α-D-glucopyranose α-D-glucosamine
- The amino sugar is named by replacing–e ending in the original name of a monosaccharide with the suffix –amine.
- There are 3 naturally occurring amino sugars. In all three, the amino group replaces the hydroxyl group at carbon 2.

CH2OH CH2OH CH2OH

O OH O O

OH OH OH NH2
OH OH OH OH OH
NH2 NH2
α-D-glucosamine α-D-galactosamine α-D-mannosamine

- Amino sugars also exist as N-acetylated form.

CH2OH

OH
OH OH
NH
I
C=O
acetyl I
CH3
N-acetyl-α-D-glucosamine

- Amino sugars and their N-acetyl derivatives are important building blocks of chitin and hyaluronic acid.
- N-acetyl derivatives of glucosamine and galactosamine acts as biochemical markers of red blood cells which distinguishes various
blood types.
- The surface of red blood cells contain glycoproteins (sugar containing proteins) that determines the blood type.

- Each blood type has specific antigens and antibodies against other blood types:
4. Sugar Phosphates
- The –OH group (usually at C1 and C6) of a monosaccharide can react with phosphoryl group to form phosphate esters. In biological
systems, phosphoryl group is usually from ATP.
CH2OH CH–O–PO32-
O OH O
OH OH
OH OH OH
OH OH
α-D-glucopyranose 6-phosphate
or simply glucose 6-phosphate

- A monosaccharide can have more than 1 phosphoryl group attached to it such as the one below:
CH2O–PO32- CH2O–PO32-–PO32-

O O

OH OH
OH O–PO32- OH OH
OH OH
α-D-glucopyranose 1,6-bisphosphate α-D-glucopyranose 6-diphosphate

- Sugar phosphates are named by stating the name of the monosaccharide first followed by a locant (numbers that determine the
position of the phosphoryl group in the structure), and then phosphate. If more than 1 phosphoryl groups are present, the prefix bis-
and di- are used. Bis- is used when the phosphoryl groups are located separately, while di- is used when the phosphoryl groups are
attached together. (See examples above.)
- Sugar phosphates are produced as intermediates in metabolism. One effect of sugar phosphorylation within cells is to trap the sugar
inside the cell; most cells do not have plasma membrane trans-porters for phosphorylated sugars. Phosphorylation also activates sugars
for subsequent chemical transformation.

5. Glycosides
- The hydroxyl group of a hemiacetal can react with an alcohol to form an acetal. This reaction is considered a dehydration synthesis
reaction since a new bond is formed with concomitant removal of H2O.

- Recall that cyclization of a monosaccharide forms a cyclic hemiacetal and hemiketal at the anomeric carbon. Thus, the pyranose
and furanose froms of monosaccharides react with alcohols in the same manner as acetal formation to form glycosides with retention
of the α and β configuration at the anomeric carbon.
CH2OH CH2OH

O O
+ CH3OH
OH Methyl alcohol OH glycosidic bond
OH OH OH O–CH3
OH OH
α-D-glucopyranose Methyl- α-D-glucopyranoside
- The new bond that is formed between the alcohol and the hydroxyl group of the anomeric carbon is known as a glycosidic bond. A
bond which involves the anomeric carbon of a monosaccharide is known as a glycosidic bond.
- Glycosides are named by stating first the alkyl group coming from the alcohol, and then mention the name of the monosaccharide.
Replace the –e in the name of the monosaccharide and replace with the suffix –ide.
III. DISACCHARIDES
- Disaccharides are carbohydrates comprising 2 monosaccharide units which are linked together via glycosidic bond. Each
monosaccharide unit is known as a residue.
- They have crystalline in appearance, imparts sweet taste, and can undergo fermentation and hydrolysis.

Formation of Disaccharides
- Recall that the –OH of the anomeric carbon of the cyclic form of a monosaccharide can react with alcohol to form glycosides.
- Disaccharides are formed in the same manner, where the –OH of the anomeric carbon of a first monosaccharide reacts with any –
OH of a second disaccharide.
- Example:

CH2OH CH2OH CH2OH CH2OH

O O O O
OH + OH OH OH
OH OH OH O
OH OH OH
OH OH OH OH
H2O
Glycosidic bond

- The illustration above shows a reaction for the formation of the disaccharide maltose. It is clear that the reaction is also dehydration
synthesis reaction since there is formation of new bond with concomitant removal of water. We shall see in the other biomolecules
that their formation also involves dehydration. The removal of water in the reaction causes the 2 monosaccharide to condensed together
forming the disaccharide.
- The new bond that is formed between the 2 monosaccharide units is also known as glycosidic bond. Notice as well that the anomer
of the first monosaccharide is retained even after the reaction.

General Structural Feature of a Disaccharide

CH2OH glycosidic
CH2OH
bond
O O
OH OH
O
OH OH
OH OH
acetal carbon hemiacetal carbon
- anomeric carbon - anomeric carbon
involved in the not involved in the
glycosidic bond glycodic bond
(not free) (free anomeric carbon)

- The structure of maltose is illustrated above. Notice that the structure possesses one free unsubstituted anomeric carbon atom
(free hemiacetal carbon). This is known as its reducing end. The anomeric carbon that is involved in the glycosidic bond (acetal
carbon) is known as non-reducing end.
- The presence of a free anomeric carbon in a disaccharide is very important in its chemistry. Disaccharides with free anomeric carbon
are reducing disaccharides, due to the fact that the free anomeric carbon has the potential to be converted to aldehyde configuration
and thus can participate in oxidation-reduction reaction of reducing sugars.
- Common monosaccharides are reducing, except for sucrose (See figure below). In the case sucrose, both of the anomeric carbons
are substituted, i.e. neither has a free anomeric carbon. Thus, it cannot participate in redox reactions of reducing sugars.
CH2OH

OH There are 2 acetal

carbons and no free
OH
anomeric carbon in
OH O this structure, as both
CH2OH anomeric carbons are
O
involved in the
glycosidic bond.
HO CH2OH

OH
Designation of Glycosidic Bonds
- The glycosidic bond also plays important role in the chemistry and physiological functions of disaccharides, and even for
polysaccharides. Some disaccharides have similar monosaccharide units, but only differ in the configuration of their glycosidic bonds.
Thus, it is important that we know how to identify the configurations of glycosidic bonds.
- Configuration of glycosidic bonds are designated like the example below for maltose:
CH2OH CH2OH
O O
OH C1 C4 OH
OH O
OH
OH OH
α(14)

- The α in the designation above indicates the type of anomer of the monsaccharide whose anomeric carbon is involved in the
glycosidic bond. The (14) indicates that the glycosidic bond is between carbon 1 (C1) of the first monosaccharide and carbon 4
(C4) of the second monosaccharide.
- Other examples:
CH2OH

O
CH2OH C4 OH
cellobiose
O O OH
OH C1 OH
OH β (14)

OH - The anomer of the monosaccharide whose anomeric carbon is involved in the

bond is β, and the glycosidic bond is between C1 and C4.
CH2OH

OH C1

OH α,β(12) sucrose
OH O
CH2OH - Both anomeric carbons of each monosaccharide involved in the bond. The α is the anomer of the
O first monosaccharide, and β is the anomer of the second monosaccharide. The glycosidic bond is
C2 between C1 and C2.
HO CH2OH

OH
Common Disaccharides
1. Maltose
- It is produced from starch (polymer of α-D-glucose produced by plants) by the action of the amylase enzymes and is a
component of malt, a substance produced by allowing barley to stoften in water and germinate. The enzyme diastase, produced
during the germination process, catalyzes the hydrolysis of starch in barley to maltose.
- It is readily fermentable by yeast, that is why it is important I brewing of beer.
- Structurally, this is a homodisaccharide of D-glucose, where the first D-glucose unit is in α anomer. The glycosidic bond is
α(14). It is a reducing disaccharide because of its free anomeric carbon.
-This can be hydrolyzed in the human body, as humans have α-glucosidase enzymes capable of hydrolyzing α glycosidic
bonds between glucose units.
D-glucose (in α anomer) D-glucose

CH2OH CH2OH
O O
free anomeric carbon
OH OH
OH O
OH
OH α(14) OH
2. Cellobiose
- It is produced from acidic hydrolysis of cellulose (polymer of β-D-glucose produced by plants).
- Structurally, this is also a homodisaccharide of D-glucose, but unlike in maltose, the first D-glucose unit is in β anomer. The
glycosidic bond is β(14). It is a reducing disaccharide because of its free anomeric carbon.
- This monosaccharide cannot be hydrolyzed in the human body, as humans have no β-glucosidase enzymes capable of
hydrolyzing β glycosidic bonds between glucose units.
D-glucose

D-glucose (in β anomer) CH2OH

O
CH2OH OH
O O OH
OH OH
OH β (14)
free anomeric carbon
OH

3. Lactose
- This is the principal carbohydrate in milk and is of critical nutritional importance to mammals in early stages of their lives.
This is considered the least sweet sugar.
- Structurally, this is a heterodisaccharide made up of D-galactose (first monosaccharide) in β anomer, and D-glucose
(second monosaccharide) via β (14) glycosidic bond. It is a reducing disaccharide because of its free anomeric carbon.
- This can be hydrolyzed in the human body, as humans have β-galactosidase enzyme capable of hydrolyzing β glycosidic
bond between galactose units.
D- glucose

D-galactose (in β anomer) CH2OH

O
CH2OH OH
OH O O OH
OH OH
β (14)

OH free anomeric carbon

4. Sucrose
- This is known as the table sugar and is produced by many higher plants. It is one of the producs of photosynthesis, which is
a heterodisaccharide made up of D-glucose (first monosaccharide) in α anomer, and D-fructose (second monosaccharide)
in β anomer.
- Both anomeric carbons are involved in the glycosidic bond, and its glycosidic bond is designated as α,β(12). This makes
sucrose a non-reducing disaccharide because it lacks free anomeric carbon.
- Sucrose is easily hydrolyzed by diluted acids, that is why jams are sweeter than table sugar. The acids in fruits hydrolyzes
the sucrose in table sugar converting it to glucose and fructose.
- This can be hydrolyzed in the human body, as humans have α-glucosidase enzymes.
CH2OH

OH D-glucose (in α anomer)

OH
OH O
CH2OH α,β (12)
O

D-fuctose (in β anomer)

HO CH2OH

OH
 Hydrolysis of Disaccharides
- Hydrolysis is the breakdown of a large molecule into simpler units in the action of water. It is a reaction that is considered to be reverse
of dehydration, because in this case water acts as a reactant.
- Disaccharides can hydrolyzed in the presence of acid or enzymes to produce corresponding monosaccharides.

CH2OH CH2OH CH2OH

CH2OH
O O O
O Acid (H+) or enzyme
OH OH + H2O OH + OH
OH O OH OH OH
OH OH
OH OH OH OH
maltose α-D-glucose α-D-glucose

- Hydrolysis of Common Disaccharides:

H+ or enzyme
1. Maltose α-D-glucose + α-D-glucose

H+ or enzyme
2. Cellobiose β-D-glucose + β-D-glucose

H+ or enzyme
3. Lactose β-D-glucose + α-D-glucose

H+ or enzyme
4. Sucrose α-D-glucose + β-D-fructose

Disaccharidases
- There are enzymes in the digestive system capable of hydrolyzing disaccharides into monosaccharides. These are known as
disaccharidases. They are secreted through, and remain associated with, luminal side of the brush border membranes of the
intestinal mucosal cells. These enzymes are responsible for the fine digestive process of carbohydrates.

- Examples of Disaccharidases:
1. Lactase – a β-galactosidase; enzyme capable of cleaving lactose due to its ability to hydrolyze β glycosidic bonds in galactose.
2. Maltase – an α-glucosidase; cleaves the α(14) glycosidic bond in maltose.
3. Sucrase-isomaltase complex – an enzyme with 2 functional subunits, the first one that cleaves the α,β(12) glycosidic bond
in sucrose; and the second one that cleaves α (16) glycosidic bond in isomaltose.

Lactose Intolerance: A Case of Digestive Enzyme Deficiency

- Lactose intolerance is a digestive disorder characterized by inability to digest lactose.This is caused by deficiency of lactase in the
body. Symptoms include bloating, diarrhea, and dehydration.

- When there is no enough lactase in the body, lactose will not be hydrolyzed into galactose and glucose; but instead, it will proceed to
the large intestine since it cannot be absorbed by the cells of the small intestine. Only monosaccharides can be absorbed by small
intestinal cells.
- As a consequence, water is drawn from the mucosa into the large intestine causing osmotic diarrhea.
- This is reinforced by bacterial fermentation of the lactose to 2-3-carbon compounds, such as acetic acid and lactic acid, plus large
volumes of CO2 and H2, causing abdominal cramps, diarrhea, and flatulence.
- Causes: genetic defect, physiological decline by age, and injuries to mucosa lining in the intestine caused by drugs or malnutrition
- Diagnosis: Oral lactose tolerance test and/or H2 gas measurement in breath
- Treatment:
1. Reduce consumption of milk or dairy products, while eating yogurts and cheeses, as well as green vegetables such as broccoli, to
ensure adequate calcium intake.
2. Use lactase-treated product.
3. Take lactase in pill form prior to eating

Sugar Substitutes
- Sucrose is the most commonly used sweetener. However, it is known to have high caloric value. That is why it is often difficult to satisfy
a demanding “sweet tooth” with sucrose without adding pounds to the body frame or inches to the waistline.
- Sugar substitutes are now used extensively as a solution to the “sucrose problem.” These are substances that impart sweet taste but
have no caloric values.
- The structures of the 3 most common sugar substitutes – saccharin, aspartame, and sucralose – are shown below:

IV. POLYSACCHARIDES
- By far the majority of carbohydrate material in nature occurs in the form of polysaccharides.
- Polysaccharides, also called glycans, consist of polymers of monosaccharides and/or their derivatives. If a polysaccharide contains
only one kind of monosaccharide molecule, it is a homopolysaccharide, or homoglycan, whereas those containing more than one
kind of monosaccharide are heteropolysaccharides.
- The most common constituent of polysaccharides is D-glucose, but D-fructose, D-galactose, L-galactose, D-mannose, L-arabinose,
and D-xylose are also common. Common monosaccharide derivatives in polysaccharides include the amino sugars (D-glucosamine
and D-galactosamine) and simple sugar acids (glucuronic and iduronic acids).

Common Properties of Polysaccharides

1. Amorphous powder in appearance
2. Does not impart sweet taste
3. Can be hydrolyzed but do not undergo fermentation
4. All polysaccharides are non-reducing although they usually have a free anomeric carbon at the end. However, this single free
anomeric carbon is not enough compared to the molecular size of a polysaccharide.
5. They have limited solubility in water due to their size, however the–OH in their structures can individually be hydrated with
water molecule resulting in a thick colloidal suspension of a polysaccharide in water.

Factors in Identifying Polysaccharides

- Polysaccharides differ in:
 nature of their component monosaccharides,
 type of glycosidic bond,
 length of their chains, and
 amount of chain branching.

Branching in Polysaccharides
- Although a given sugar residue has only one anomeric carbon and thus can form only one glycosidic linkage with hydroxyl groups
on other molecules, each sugar residue carries several hydroxyls, one or more of which may be an acceptor of glycosyl substituents.
This enables polysaccharides to form branches (See figure below). This ability to form branched structures distinguishes
polysaccharides from proteins and nucleic acids, which occur only as linear polymers.
Types of Polysaccharides
- Polysaccharides function as storage material, structural components, or protective substances. We can use these functions to
classify our polysaccharides.

A. Storage Polysaccharides
- These polysaccharides function as storage forms of monosaccharides and are used as energy source in cells. Monosaccharides
are often stored in the cell as polysaccharides to lower osmotic pressure inside the cell.
- The most important storage polysaccharides are your starch and glycogen.

Starch
- It is by far the most common storage polysaccharide in plants. This is a homopolysaccharide of α-D-glucose units and contains only
α-linkages in between glucose units which give rise to a chain that folds in a helical form.

- Starches are composed of 2 types of glucose polymers – amylose and amylopectin:

1. Amylose
- This is the minor component of starch which only accounts for 10-20%. It can solubilize when treated with boiling water.
- Structurally, it composed of 300-500 glucose units with α(14) glycosidic bonds forming an unbranched long chain with
a molecular weight of 400,000 Da or more.

2. Amylopectin
- This is the major component and accounts for 80-90% of starch. It cannot be dissolved in boiling water, but instead forms
paste-like gel.
- Structurally, it is highly branched, unlike amylose, with molecular weight more than 1 million Da. The linear glucose units
in amylopectin is also linked by α(14) glycosidic bonds, and the branching involves α(16) glycosidic bonds.

- Notice that all glycosidic bonds between each glucose units in amylose and amylopectin are α type. This is the reason why starch
has nutritional value in humans as we have enzymes capable of hydrolyzing α linkages in glucose units (α-glucosidase).
- In animals, digestion and use of plant starches begin in the mouth with α-salivary-amylase, the major enzyme secreted by the salivary
glands. Although the capability of making and secreting salivary α-amylases is widespread in the animal world, some animals (such as
cats, dogs, birds, and horses) do not secrete them. Salivary α-amylase is an endoamylase that splits α(1→4) glycosidic linkages only
within the chain. Raw starch is not very susceptible to salivary endoamylase. However, when suspensions of starch granules are
heated, the granules swell, taking up water and causing the polymers to become more accessible to enzymes. Thus, cooked starch is
more digestible. Most starch digestion occurs in the small intestine via pancreatic α-amylase.

Glycogen
- This is also known as animal starch as this is the major form of storage polysaccharide in animals. It is found mostly in liver cells and
muscle cells in humans.
- Liver glycogen is a homopolysaccharide of α-D-glucose units which has similar structure as amylopectin. All glycosidic linkages are
α(14) and α(16) linkages; but glycogen is more branched than amylopectin.

Amylopectin Glycogen
- When glucose in blood is present in excess amount, liver and muscle cells convert the excess glucose to glycogen. When glucose
level drops, some of the stored glycogen are hydrolyzed back to glucose.

B. Structural Polysaccharides
- These polysaccharides serve as structural component in plant cell walls and animal exoskeletons.
- The most important structural polysaccharides are cellulose and chitin.

Cellulose
- This is the most abundant naturally occurring polymer in the world. Found in the cell walls of nearly all plants, cellulose is one of the
principal component providing physical structure and strength. The wood and bark of trees are insoluble, highly organized structures
formed from cellulose. It is awe-inspiring to look at a large tree and realize the amount of weight supported by polymeric structures
derived from sugars.
- Cellulose, aside from strength, also has delicate side. Cotton, whose woven fibers make some of our most comfortable clothing fabrics,
is almost pure cellulose. Derivatives of cellulose have found wide use in our society. Cellulose acetates are produced by the action
of acetic anhydride on cellulose in the presence of sulfuric acid and can be spun into a variety of fabrics with particular properties.
Referred to simply as acetates, they have a silky appearance, a luxuriously soft feel, and a deep luster and are used in dresses,
lingerie, linings, and blouses.
- Structurally, it is similar to amylose being a linear homopolysaccharide of D-glucose units. The structural difference, which
completely alters the properties of the polymer, is that in cellulose the glucose units are linked by β(1→4) glycosidic bonds, whereas in
amylose the linkage is α(1→4). The conformational difference between these two structures is shown in below

- The α(1→4) linkage sites of amylose are naturally bent, conferring a gradual turn to the polymer chain, which results in the helical
conformation already described. On the other hand, the β(14) linkages in cellulose give rise to a long linear chain, referred to as
an extended ribbon. Juxtaposition of several such chains permits efficient inter-chain hydrogen bonding, the basis of much of the
strength of cellulose.

- Although cellulose is a polymer of glucose, it does not have nutritional value to humans, because we lack β-glucosidase enzymes
capable of hydrolyzing β linkages between glucose units. The intestinal tracts of grazing animals such as cows and sheep, however,
have bacteria that produce enzyme cellulase (a β-glucosidase).
- Despite its indigestibility, cellulose is still an important component of a balanced diet as dietary fibers. They serve as roughage in
the excretion of digestive wastes.

Chitin
- This is a polysaccharide similar to cellulose, both in biological function and three-dimensional structure. Chitin is present in the
cell walls of fungi and is the fundamental material in the exoskeletons of crustaceans, insects, and spiders. The structure of chitin
is an extended ribbon identical to that of cellulose, except that the -OH group on each carbon 2 is replaced by –NHCOCH3, so the
repeating units are N-acetyl-D-glucosamines in β(14) linkages.

- Like cellulose, the chains of chitin can be packed side by side in a crystalline, strongly hydrogen-bonded form.
- Chitin is the earth’s second most abundant carbohydrate polymer (after cellulose), and its ready availability and abundance offer
opportunities for industrial and commercial applications. Chitin-based coatings can extend the shelf life of fruits, and a chitin
derivative that binds to iron atoms in meat has been found to slow the reactions that cause rancidity and flavor loss. Without such
a coating, the iron in meats activates oxygen from the air, forming reactive free radicals that attack and oxidize polyunsaturated lipids,
causing most of the flavor loss associated with rancidity. Chitin-based coatings coordinate the iron atoms, preventing their interaction
with oxygen.

C. Glycosoaminoglycans
- These are also known as acidic polysaccharides or mucopolysaccharide. They are involved in intracellular and extracellular
functions. They are usually a heteropolysaccharide containing alduronic acids and amino sugars, where one or both monosaccharide
components has a negative charge due to the presence if sulfate group or carboxyl group.
- Solutions of glycosoaminoglycans have slimy, mucus-like consistency that results from their high viscosity and elasticity.
- Two of the most well-known acidic polysaccharides are hyaluronic acid and heparin.

Hyaluronic acid
- This present in connective tissues, tendons, synovial fluid, and vitreous humor. It contains alternating residues of N-acetyl-β-D-
glucosamine (NAG) and D-glucuronate (conjugate base of D-glucuronic acid).
- The glycosidic bonds in hyaluronic acid are alternating β(13) and β(14).

β(13) β(14)

- Hyaluronic acid is an extended, rigid molecule whose numerous repelling anionic groups bind cations and water molecules. In
solution, hyaluronic acid occupies a volume ∼1000 times that in its dry state. Hyaluronic acid solutions have a viscosity that is shear
dependent (an object under shear stress has equal and opposite forces applied across its opposite faces). At low shear rates, hyaluronic
acid molecules form tangled masses that greatly impede flow; that is, the solution is quite viscous. As the shear stress increases, the stiff
hyaluronic acid molecules tend to line up with the flow and thus offer less resistance to it. This viscoelastic behavior makes hyaluronic
acid solutions excellent biological shock absorbers and lubricants.
- Hyaluronic acid has an unanticipated property. The naked mole rat is a hairless, mouse-sized rodent (it resembles a pink sausage with
teeth) that has a longer life span (>30 years) than any other rodent. This is, in part, because cancer has never been observed in naked
mole rats (in contrast, mice and rats, which live ∼4 years, have a high incidence of cancer). Naked mole rat cells secrete extremely high
molecular mass hyaluronic acid. This interferes with the signaling pathways that support malignant transformation. Consequently,
reducing the amount of high molecular-mass hyaluronic acid in a culture of naked mole rat cells by either mutationally under-expressing
the enzyme that synthesizes the hyaluronic acid or overexpressing the enzyme that degrades it yields cells that are susceptible to
malignant transformation.

Heparin
- This is a blood anticoagulant which are naturally present in mast cells and is released at the site of tissue injury. This is also commonly
used as anticoagulant when taking blood for clinical studies. Commercial heparin is obtained from slaughterhouse animal lung tissues
(pigs and cows)
Structurally, it contains alternating unit of D-glucuronate-2-sulfate and N-sulfo-D-glucosamine-6-sulfate
- The repeating units are linked by α(14) glycosidic bonds.
- In contrast to the other glycosaminoglycans, heparin is not a constituent of connective tissue but occurs almost exclusively in the
intracellular granules of the mast cells that occur in arterial walls. It inhibits the clotting of blood, and its release, through injury, is
thought to prevent runaway clot formation. Heparin is therefore in wide clinical use to inhibit blood clotting—for example, in postsurgical
patients.

Hydrolysis of Starch
- Like disaccharides, polysaccharides are also capable of hydrolysis. Hydrolysis of starch is an important process in the digestion of
carbohydrates in humans, as starch is our primary source of energy.
- Starch can also be hydrolyzed by acids and enzymes.

A. Acidic Hydrolysis of Starch

- When starch is heated with a strong acid, it will produce small fragments gradually.

Starch Amylodextrin Erythrodextrin Achrodextrin Maltose

B. Enzymatic Hydrolysis of Starch

- Enzymatic hydrolysis of starch is carried out in the of amylases. Amylase is an enzyme capable of attacking the α(14) glycosidic
bond in starch.
- There are 2 types of amylases – α-amylase and β-amylase. Note that the α and β in amylases do not signify anomeric forms in
this case.

Action of Amylase

 β-amylase
- β-amylase is an exoglycosidase that cleaves starting from the glucose ends of starch releasing maltose consecutively. When
𝛽-amylase acts on amylopectin, maltose units are liberated from the ends of the branches of amylopectin, until the
action of enzyme is blocked at the α(16) glycosidic linkage.
- The action of 𝛽-amylase stops at branching points, leaving a large molecule, called limit dextrin or residual dextrin.
- β-amylase is not present in humans, it is present in plants (germinating seeds and ripening fruits).

 α-amylase
- Salivary amylase and pancreatic amylase in humans are both α-amylase. α-amylases act randomly on α(14) glycosidic
linkages to split starch into smaller units (dextrins) and finally to maltose.
- Chemical digestion of starch starts in the mouth by the action of salivary amylase resulting in branched and unbranched
oligosaccharides (dextrin), and some maltose.
- Salivary digestion occurs briefly though, because it is interrupted by the acidic environment of the stomach.
- When the acidic stomach contents reach the small intestine, they are neutralized by bicarbonate secreted by the pancreas, and
pancreatic α-amylase continues the process of starch digestion.
- Digestion by pancreatic amylase results in maltose.
- The final digestive processes occur primarily at the mucosal lining of the upper jejunum, and include the action of several brush-
border enzymes (disaccharidase).