Carbohydrates

Carbohydrates are macronutrients and one of the three primary energy sources for our bodies.
Carbohydrates are so-called because they are chemically composed of carbon, hydrogen, and
oxygen. Carbohydrates, which include sugars, fibres, and starches, are necessary nutrients.
They're in cereals, vegetables, and fruits, as well as milk and other dairy products. They are the
primary dietary types that are essential for living a healthy life.

Types of Carbohydrates

Types of Carbohydrates
Complex carbohydrates are frequently made up of single units (monosaccharides) that are linked
together. Two monosaccharides combine to form a disaccharide. Examples of carbohydrates
having two monomers include- Sucrose, Lactose, Maltose, etc. Oligosaccharides comprise two to
ten simple sugar units. Polysaccharides comprise hundreds of thousands of linked
monosaccharides. Complex carbs provide somewhat sustained energy.
Monosaccharides
One example of a carbohydrate monomer or monosaccharide is glucose. Mannose, galactose,
fructose and other monosaccharides are other examples. Monosaccharide structural organisation
is as follows:

Disaccharides
Two monosaccharides combine to form a disaccharide. Examples of carbohydrates having two
monomers include- Sucrose, Lactose, Maltose, etc.

Oligosaccharides
Carbohydrates formed by the condensation of 2-9 monomers are called oligosaccharides. By this
convention, trioses, pentoses, hexoses are all oligosaccharides.

Polysaccharides
Polysaccharides contain long monosaccharide units joined together by glycosidic linkage. Most
of them act as food storage for e.g. Starch. Starch is the main storage polysaccharide for plants. It
is a polymer of α glucose and consists of two components-Amylose and Amylopectin. Cellulose
is also one of the polysaccharides that are mostly found in plants. It is composed of β-D- glucose
units joined by a glycosidic linkage between C1 of one glucose unit and C4 of the next glucose
unit.

Functions of Carbohydrates
• Carbohydrates' primary job is to provide energy and food to the body and nervous system.
• Carbohydrates, which include sugars, starch, and fibre and are abundant in grains, fruits,
and milk products, are recognised as one of the basic components of diet.
• Carbs are also referred to as starch, simple sugars, complex carbs, and other terms.
• It also helps with fat metabolism and prevents ketosis.
• Proteins are the primary source of energy, hence this inhibits their breakdown for energy.
• Amylase, an enzyme, aids in the breakdown of starch into glucose, which is then converted
into energy for metabolism.
Carbohydrate Metabolism
Starch contains a lot of dietary glucose. Amalyses are enzymes that help with metabolism by
degrading starch. Lactose (from milk), fructose (from fruits), and sucrose (from table sugar) are
all sources of glucose. Active membrane transport mechanisms aid in the absorption of
monosaccharide species such as fructose, glucose, and fructose. Special intestine glucosidases
divide disaccharides to create monosaccharide components.

What is Glycolysis?
Glycolysis is the process of breaking down glucose to produce energy. It generates two pyruvate
molecules, ATP, NADH, and water. The process occurs in a cell's cytoplasm and does not require
oxygen. It can be found in aerobic and anaerobic organisms.
Stage 1
A phosphate group is added to glucose in the cell cytoplasm, by the action of enzyme hexokinase.
In this, a phosphate group is transferred from ATP to glucose forming glucose,6-phosphate.
Stage 2
Glucose-6-phosphate is isomerised into fructose,6-phosphate by the enzyme phosphoglucomutase.
Stage 3
The other ATP molecule transfers a phosphate group to fructose 6-phosphate and converts it into
fructose 1,6-bisphosphate by the action of the enzyme phosphofructokinase.
Stage 4
The enzyme aldolase converts fructose 1,6-bisphosphate into glyceraldehyde 3-phosphate and
dihydroxyacetone phosphate, which are isomers of each other.
Step 5
Triose-phosphate isomerase converts dihydroxyacetone phosphate into glyceraldehyde 3-
phosphate which is the substrate in the successive step of glycolysis.
Step 6
This step undergoes two reactions:
The enzyme glyceraldehyde 3-phosphate dehydrogenase transfers 1 hydrogen molecule from
glyceraldehyde phosphate to nicotinamide adenine dinucleotide to form NADH + H+
Glyceraldehyde 3-phosphate dehydrogenase adds a phosphate to the oxidised glyceraldehyde
phosphate to form 1,3-bisphosphoglycerate.

Step 7
Phosphate is transferred from 1,3-bisphosphoglycerate to ADP to form ATP with the help of
phosphoglycerokinase. Thus two molecules of phosphoglycerate and ATP are obtained at the end
of this reaction.

Step 8
The phosphate of both the phosphoglycerate molecules is relocated from the third to the second
carbon to yield two molecules of 2-phosphoglycerate by the enzyme phosphoglyceromutase.
Step 9
The enzyme enolase removes a water molecule from 2-phosphoglycerate to form
phosphoenolpyruvate.
Step 10
A phosphate from phosphoenolpyruvate is transferred to ADP to form pyruvate and ATP by the
action of pyruvate kinase. Two molecules of pyruvate and ATP are obtained as the end products.
 Fig: Diagram of Glycolysis pathway

TCA cycle
TCA cycle or Tricarboxylic Cycle is also known as Kreb’s Cycle or Citric Acid Cycle. It is the
second stage of cellular respiration that occurs in the matrix of mitochondria. All the enzymes
involved in the citric acid cycle are soluble. It is an aerobic pathway because NADH and FADH2
produced transfer their electrons to the next pathway which will use oxygen. If the transfer of
electrons does not occur, no oxidation takes place. Very little ATP is produced during the process
directly. The TCA cycle is a closed loop. The last step of the pathway regenerates the first
molecule of the pathway.

Steps of TCA Cycle

The following are the important steps of the TCA cycle:
Step 1
Acetyl Co-A combines with a four-carbon compound, oxaloacetate, and releases the CoA group
resulting in a six-carbon molecule called citrate.
Step 2
In the second step, citrate gets converted to isocitrate, an isomer of citrate. This is a two-step
process. Citrate first loses a water molecule and then gains one to form isocitrate.
Step 3
The third step involves oxidation of isocitrate. A molecule of carbon dioxide is released leaving
behind a five-carbon molecule, ɑ-ketoglutarate. NAD+ gets reduced to NADH. The entire process
is catalyzed by the enzyme isocitrate dehydrogenase.
Step 4
Here, ɑ-ketoglutarate is oxidized reducing NAD+ to NADH and releasing a molecule of carbon
dioxide.CoA is picked up by the remaining four-carbon molecules forming an unstable compound
succinyl CoA. ɑ-ketoglutarate dehydrogenase catalyzes the entire process.
Step 5
CoA from succinyl CoA is replaced with a phosphate group. It is then transferred to ADP to make
ATP. Succinate, a four-carbon molecule is produced in this step.
Step 6
Succinate is oxidized to fumarate. Two hydrogen atoms are transferred to FAD to produce FADH2.
FADH2 transfers its electrons directly to the electron transport chain since the enzyme carrying
out the reaction is embedded in the inner membrane of mitochondria.

Step 7
A water molecule is added to fumarate which is then converted to malate.
Step 8
The oxidation of malate regenerates oxaloacetate, a four-carbon compound, and another molecule
of NAD+ is reduced to NADH in this step.
 Fig: Steps of TCA cycle
End Products of TCA Cycle
• 6 NADH
• 2 ATPs
• 2 FADH2

Pentose Phosphate pathway

The hexose monophosphate (HMP) shunt, also known as the pentose phosphate pathway or phosphogluconate
pathway, is a metabolic pathway that runs parallel to glycolysis. This pathway produces NADPH and
intermediates required for the synthesis of nucleic acids and amino acids.

Features of the HMP Shunt

• It is an anabolic pathway that takes place in the cytosol for most organisms. However, in
plants, it takes place in plastids.
• The pathway takes place in two distinct phases: oxidative and non-oxidative phases.
• The reactions of this pathway are enzyme catalysed.
• The products obtained from the pathway include NADPH, which is used in biosynthesis in cells,
ribose-5-phosphate, which is used in the synthesis of nucleic acid and nucleotides, and erythrose-
4-phosphate, which is used for the synthesis of aromatic amino acids.
• In humans, this pathway is most active in mammary glands, adrenal cortex, adipose tissue,
erythrocytes, testes and liver.
• The HMP shunt is a tightly controlled metabolic pathway that is connected with other pathways,
such as glycolysis and gluconeogenesis, depending upon the metabolic needs of the body.
• Defects in the hexose monophosphate pathway can be linked to several disorders.
Epimers
Epimer in stereochemistry specifies one of a pair of stereoisomers. At the stereogenic centre,
two isomers present in the molecule differ, while the rest remains identical. A molecule may
contain numerous stereocenters leading to several stereoisomers.

Anomers
An anomer is actually an epimer (also a cyclic saccharide) that differs in configuration, particularly
at the acetal or hemiacetal carbon. The anomers are Saccharides or glycosides that are epimers,
which are distinct from each other in configuration at C-2. For example, the anomers of D-Glucose
is α-D glucopyranose and β-D Glucopyranose which differ in configuration at C-2. Chemistry
Glossary.
Dextro and Levo
Diastereomers are stereoisomers that are not mirror images of each other in that they are not
linked with reflection operation unlike of enantiomers. They possess the same physical
properties.

Fig: Dextro, Right(d) Fig: Levo left (l)

Fischer projections

Emil Fischer, a German scientist who won the Nobel Prize in Chemistry in 1902, invented the Fischer
projection in 1891. A Fischer projection depicts the carbohydrate in its open chain form rather than its
cyclical form. Carbon atoms in the carbohydrate molecule's primary chain are joined vertically,
whereas hydrogen atoms and hydroxyl groups are bonded horizontally. The horizontal lines depict
bonds that emerge from the page, whereas the vertical lines depict bonds that are contained within the
page. A Fischer projection may or may not include carbon atoms. Fischer projections have one main
advantage: it is easy to visually identify the stereochemical properties of a carbohydrate and compare
the difference between two carbohydrates quickly and easily.

Haworth projections

We have already talked about Fischer projection formulas for representing the cyclic forms of D-
glucose. However, Haworth thought that these structures were awkward. He developed the hexagonal
representations, which resembled the heterocyclic pyran containing five carbon and one oxygen in the
ring. He came up with the names alpha-D-glucopyranose and beta-D-glucopyranose for the hexagonal
structures of alpha-D-glucose and beta-D-glucose.
Properties of Glucose

• It has a molecular formula of C6H12O6.

• When HI is heated for a long time, n-hexane is formed which indicates that all the six carbon
atoms are linked in a straight chain.
• The oxime is formed when glucose reacts with hydroxylamine and cyanohydrins on the addition
of hydrogen cyanide to it. This reaction can confirm the presence of the carbonyl group in
glucose.
• On the reaction of glucose with a mild oxidizing agent like bromine water, the glucose gets
oxidized to a carboxylic acid that contains six carbon atoms. This indicates that the carbonyl
group is present as an aldehyde group.
• The presence of -OH group is confirmed after the acetylation of glucose with acetic acid, which
gives glucose pentaacetate.
• Glucose as well as gluconic acid both yields dicarboxylic acid and saccharic acid on oxidation
with nitric acid. The presence of primary alcohol is indicated by this.

C6H12O6 Glucose

Molecular Weight/ Molar Mass 180.16 g/mol

Density 1.54 g/cm³

Melting Point 146 °C

Simple sugar Monosaccharide

Chemical properties of glucose

1. Glucoside formation
Glucose reacts with methanol in the presence of HCl and gives α and β glucoside. Glucoside
formation is due to the reaction of alcohol with glucoside -OH group of glucose. β, D glucose is
forms β, D-methyl glucoside. In the same way, fructose forms fructoside.

2. Oxidation
Glucose when treated with bromine water, forms gluconic acid. The aldehyde group is oxidised to
carboxylic group.
Br2 + H2O < - - - > HOBr + HBr
First, bromine forms hypobromous acid (HOBr), with water and oxidises the glucose to gluconic
acid.When glucose is oxidised with nitric acid, saccharic acid is formed. When glucose is oxidised
with hydrogen peroxide (H2O2), glucuronic acid is formed. In this reaction only the primary
alcohol is converted into carboxylic group, whereas the aldehyde remains unchanged.
3. Reaction with concentrated H2SO4
Glucose is treated with concentrated H2SO4 or HCl, and forms 5, hydroxymethyl furfural which
on further heating yields levulinic acid and formic acid.This reaction is the basis of the colour test,
known as Molish test for sugars. When pentoses are treated with mineral acids furfural is obtained
on heating.

4. Ester formation
They can form esters with carboxylic acids due to the presence of OH groups. For eg. glucose
reacts with five molecules of acetic anhydride to form penta acetate derivative. It obviously
indicates that the glucose contain five OH groups.

5. Osazone formation
An important reaction of reducing sugars, (monosaccharide and disaccharrides) having potential
aldehyde or ketone group, is their action with phenylhydrazine to form phenyl hydrazones.
Reaction with phenylhydrazine involves only 2 carbon atoms namely the carbonyl carbon atom
and the adjacent one.

The steps involved in phenylhydrazine reactions are

1. One molecule of glucose condenses with one molecule of phenyl hydrazine to form soluble
glucose phenylhydrazone.
2. In the presence of excess of phenylhydrazine, another molecule of phenylhydrazine enters
the reaction.
3. Now the third molecule of phenylhydrazine enters the reaction, giving rise to phenyl
glucosazone which are yellow coloured crystals.

6. Mutarotation
Mutarotation is the change in optical rotation caused by a shift in the equilibrium between two
anomers when their stereocenters interconvert. Mutarotation occurs in cyclic sugars when the and
anomeric forms interconvert. The optical rotation of the solution is determined by the optical
rotation of each anomer in the solution and their ratio.
Properties of Protein
• Solubility: Instead of true solutions in water, proteins form colloidal solutions. This is
because of the large volume of protein molecules.
• Molecular weight: Proteins differ according to their molecular weights, which depend on
the amount of residues of amino acids.
• Isoelectric pH: Isoelectric pH was defined as a property of amino acids.
• The pH of a protein is determined by the structure of the amino acids (especially its
ionizable groups). The pl is highly determined by acidic amino acids (asp, glu) and
fundamental amino acids (his, lys, arg).
• Protein occurs as tweeters or dipolar ions in Isoelectric pH. They have limited solubility,
maximum precipitability, and less buffer potential in electrically neutral (do not migrate in
the electrical field).
• Acidic and essential proteins (e Lys + e Arg)/e Glu + e Asp): proteins of which the ratio is
higher than 1 are referenced as fundamental proteins. The ratio is less than 1. For acidic
proteins.
• Protein precipitation: In colloidal solution, proteins occur due to polar group hydration (-
COO, -NH3, -OH).
• Dehydration or neutralization of polar groups may precipitate proteins.
• Precipitation at pH: Proteins are less soluble at isoelectric pH in general. When the pH
is changed to pH (4.6 for casein), some proteins (e.g. casein) readily precipitate. Curd
production from milk is a great example of sluggish milk protein precipitation, casein at
 pl. This is attributable to the lactic acid formed by the fermentation of bacteria that lowers
the casein pH to pl.
• Precipitation by salting out: The protein precipitation process is known as salting out by
adding neutral salts such as ammonium sulfate or sodium sulfate. This phenomenon is
clarified on the basis of salt dehydration of protein molecules. This induces intensified
protein interaction, resulting in precipitation and molecular aggregation.
• The amount of salt needed for the precipitation of proteins depends on the protein
molecule’s size (molecular weight).