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Chromatography

By Dr Ashish Agravatt

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Chromatography

  • Term chromatography is derived from Greek word meaning ‘colored writing’.
  • First used by Russian botanist Tswett in 1903.

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Introduction of Chromatography

Definition

Chromatography is a separation technique based on the different interactions/diiferential distribution of compounds with two phases, a mobile phase and a stationary phase, as the compounds travel through a supporting medium.

Components:

mobile phase: a solvent that flows through the supporting medium

stationary phase: a layer or coating on the supporting medium that interacts with the analytes

supporting media: a solid surface on which

the stationary phase is bound or coated

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Types of Chromatography…

Paper

HPLC

Gas

Thin layer

Column

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Types of chromatography

  • In column chromatography the stationary phase is contained in a tube called the column.

  • Planar chromatography. In this type the stationary phase is coated on a planar structure

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Paper chromatography

Stationary phase:

Paper Whatman paper 1 or 3 DEAE Cellulose (Diethylaminoethyl) CM Cellulose (Carboxy methyl)

Mobile phase: Mixture of organic solvants, water & additatives.

Ascending & descending chromatography.

Amino acids, sugars and some drugs or chemicals separated.

Diagnosis of Aminoacidurias (Phenylketouria, Alkaptonuria etc.

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∙ ∙ ∙

∙ ∙ ∙

Paper

Strip

Mobile

Phase

Mobile

Phase

PAPER CHROMATOGRAPHY

ASCENDING

DESCENDING

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  • Visualization of chromatography:-
  • After the chromatographic run is over, paper is dried, it is sprayed with a location reagent.
  • Appear as discrete spots.
  • Ninhydrin for amino acids & proteins
  • Sulphuric acid for phospholipids
  • Diphenylamine for sugars.

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DETECTION

"Rf value is the ratio of distance travelled by

the solute to the distance

travelled by the solvent front

Distance travelled by solute

Rf = Distance travelled by solvent front

  • if a compound travels 2.1 cm and the solvent front travels 2.8 cm,(2.1/2.8) , the Rƒ value = 0.75

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THIN LAYER CHROMATOGRAPHY

Calculation of Rf’s

The Rf is defined as the distance the center of the spot moved divided by the distance the solvent front moved (both measured from the origin)

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Thin layer chromatography

Adsorption TLC

Stationary phase: Silica gel, Alumina

  • Mobile phase: Mixture of organic solvents,

water & additatives.

Differential adsorption & partition coefficient of components between stationary & mobile phase.

Eg. Phospholipids and pigments.

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COLUMN CHROMATOGRAPHY

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Column Chromatography

Stationary phase is held in a narrow tube through which the mobile phase is forced under pressure or under the effect of gravity

Column chromatography is generally used as a purification technique

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MOBILE PHASE

STATIONARY PHASE

ELUTE

COLUMN CHROMATOGRAPHY

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Columnar Chromatography (CC)

The stationary phase is packed into a column.

The mobile phase is a moving liquid or gas.

  • Liquid Column Chromatography
  •   Gas Column Chromatography

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Liquid chromatography

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SEPARATION MECHANISMS

1- Adsorption chromatography.

2- Partition chromatography.

3- Ion exchange chromatography.

4- Gel filtration chromatography.

5- Affinity chromatography

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Principle of separation�

  1. Adsorption chromatography.

Chromatography in which separation is based mainly on differences between the adsorption affinities of the sample components for the surface of an active solid.

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Image Source : Biochemistry by Dr DM Vasudevan

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Ion-exchange Chromatography

Separation is based on an exchange of ions between a charge stationary surface and mobile phase of opposite charge. (Between surface and eluents).

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-

Operationally, the particle surfaces of a plastic resin or silica serve as the stationary phase to which funtional groups with fixed cationic or anionic charges are bounded.

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Cation-exchange particle- contains covalently

bound negatively charge functional groups.

  • Use to separate or exchange cationic solutes.
  • Examples-

* Strong acidic groups- sulphonate ions.

* weak acidic groups – carboxylate ions

- phosphate(p)

- sulfomethyl

- sulfoethyl

- sulfopropyl

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Anion- exchange packing

they are strongly basic quaternarly

amines with positive charges.

Used to separate anionic solutes.

Examples- triethylaminoethyl groups

or

Weakly basic groups – such as

* aminoethyl(AE)

* diethylaminoethyl (DEAE)

* guanidoethyl(GE).

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Image Source : Biochemistry by Dr DM Vasudevan

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Clinical application:-

-Separation of aminoacids, peptides,

proteins , nucleotides, oligonucleotides

and nucleic acid.

- Separation and removal of inorganic ions from aqueous mixtures.

*Most water purification units used to prepared deionized water for the laboratory contains “ mixed-bed” columns of cations and anion resins.

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Gel-Filteration Chromatography

Also known as

* Size-Exclusion Chromatography

* Gel- Permeation Chromatography

* Molecular seive Chromatography

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Separation of the basis of their

molecular size.other factors are

molecular shape & hydration.

- Beads of these materials are porous with

pore size that allow small molecules to

be temporarily entrapped.

-Too larger molecules do not enter pores

remain entirely in the mobile phase

and are rapidly eluted from columns.

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Image Source : Biochemistry by Dr DM Vasudevan

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Stationary phase :- include

* cross-linked dextran

* agarose

* porous glass

* polyacrylamide

* polystryrene-divinylbenzene

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Applications of GPC to natural products

Determination of M. wt. of peptides, proteins & polysaccharides.

Separation of mixture of mono- & polysaccharides.

Separation of amino acids from peptides & proteins.

Separation of proteins of different molecular weights.

Separation of myoglobin & haemoglobin.

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Affinity Chromatography

Separtion is based unique and specific biological interaction of the analytes and ligand is used for the separtion.

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Affinity chromatography

  • Enzyme-substrate, Antigen-Antibody, Hormone-receptor

  • The beads in column have a covalently attached chemical group
  • A protein with affinity for this particular chemical group will bind to the beads in column and its migration will be retarded

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Image Source : Biochemistry by Dr DM Vasudevan

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Clinical application:-

*To separate and prepare larger

quantities of protein and antibodies

for futher study.

*Cells with different suface carbohydrate moietes are seperated by lectin columns.

*Low-density and very low density lipoprotein are separated with heparin columns.

*Glycated hemoglobins are separated with phenylboronate columns.

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Gas Chromatography

Developed by James and martin

in 1952 to separate fatty acids.

Gaseous mobile phase is used to pass a mixture of volatile solutes through a column containing stationary phase.

Here mobile phase is a typically inert gas such as – nitrogen, helium, hydrogen or agron .

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Image Source : Biochemistry by Dr DM Vasudevan

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  • Solute seperation based on the relative

differences in the solutes vapour pressures

and interactions with the stationary phase.

  • More volatile solutes elutes from the column

before a less volatile one.

  • The column effluent carries separated solutes to

the dectector in the order of their elution.

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  • The solutes are identified by

their similar retension times.

  • Peak size is directly proportional to the amount of the solute dectected and is used to quantify it.

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Subclassification

GSC

Seperation occurs primarily by differences in adsorption at the solid phase surface.

GLC

Separation is based on differences in solute partitioning between the gaseous mobile phase and liquid stationary phase.

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HPLC

When the particles of small diameters are

used as the stationary phase support the

technique is known as HPLC

Here column efficiency is inversely related to the column packing particle size and pressure drop is related to the square of the particle diameter, relatively high pressure are required to pump liquids through efficient HPLC columns.

Most widely used form of LC.

.

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High pressure use to pump the mobile phase through

a tightly packed column. (5000 – 10,000psi).

  • High pressure pumps =>speed the movement of protein molecule down the column
  • By reducing transit timeon column , HPLC can limit diffuse spreading of protein bands and thus greatly improve precision

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Detectors are ultraviolet absorptimeter.

⮫ Purified fraction of sample mixture recovered.

⮫ High speed, high resolution and versatility.

⮫ Use estimation and detection of hormone -

eg. Epinephrine, nor-epinephrine, ACTH,

Vitamin-A, Calcitriol

Drugs – Phenytoin, Phenobarbitone.

Metabolites – Metanephrins.

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Instrumentation

  • Instruments required:
    • Mobile phase reservoir
    • Pump
    • Injector
    • Column
    • Detector
    • Data system

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LC column

LC injector

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MCQ 1

  • Which of the following separation technique is based on molecular size of protein

  • A Chromatography based on carboxymethyl cellulose column
  • B Chromatography based on Diethylaminoethyl cellulose column
  • C Affinity chromatography using nickel column
  • D Gel filteration chromatography using porous beads

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MCQ 2

  • Methods of chromatography in which molecules are separated based on charges is :
  • A Affinity chromatography
  • B Ion exchange chromatography
  • C Adsorption chromatography
  • D Size exclusion chromatography

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