MEDICAL CHEMISTRY 2025-26: PROTEIN ANALYSIS

Lecture Overview

  • Instructor: G. Simos
  • Date: 26.11.2025
  • Topics Covered:
    • Isolation and purification of proteins
    • Determination of molecular weight (MW) and isoelectric point (pI)
    • Detection and quantification of proteins
    • Determination of amino acid sequences
    • Protein activity determination methods

Key Questions Addressed

  1. How can a protein be isolated?
  2. How is the MW and pI of a protein determined?
  3. How is a protein detected and quantified?
  4. How is the amino acid sequence of a protein determined?
  5. What methods exist for protein activity determination?

Protein Isolation/Purification/Analysis Methods

  • Methods include
    • Differential centrifugation
    • Salting out
    • Dialysis
    • Column chromatography (molecular exclusion, ion-exchange, affinity)
    • Electrophoresis (SDS-PAGE, isoelectric focusing, two-dimensional)
    • Immunological methods (antibody structure and function, preparation of monoclonal antibodies, immunoprecipitation, ELISA, immunoblotting, immunochromatography)
    • Determination of amino acid sequence (Edman degradation, mass spectroscopy)

Learning Goals

  • To achieve success, students must have a solid understanding of:
    • Basic principles of protein isolation, purification, and analysis methods
    • Basic principles of immunological techniques
    • Basics of amino acid sequencing methodology

Suggested Reading

  1. Tymoczko, Berg, Stryer: Biochemistry: A Short Course, Ch. 5
  2. Berg, Tymoczko, Stryer: Biochemistry, Ch. 3
  3. Nelson, Cox: Lehninger’s Principles of Biochemistry, Ch. 3
  4. Alberts et al.: Molecular Biology of the Cell, 5th Ed., Ch. 8
  5. Alberts et al.: Essential Cell Biology, 5th Ed., Ch. 4

Exploring Protein Function

Steps in Studying Protein Function
  1. Isolation and purification of the protein
  2. Determination of the amino acid sequence
  3. Development of antibodies and localization within cells/tissues
  4. Determination of the tertiary structure
The Proteome
  • Definition: The complete set of proteins expressed under specific conditions, their functions, and interactions.
  • Dynamic Nature: The proteome changes based on cell type, developmental stage, environmental conditions, etc.
  • Required for understanding cellular functions and consists of approximately 100,000 proteins in humans.
Proteomics
  • Definition: Systematic analysis of the proteome in contrast to genomics.
  • Proteins can be purified based on unique properties like solubility, size, charge, and affinity for other molecules.
Determining Protein Activity
  1. Develop a protein activity determination method (assay).
  2. Measure total protein to ascertain the activity of the protein of interest.
    • Specific Activity Formula: ( ext{Specific Activity} = \frac{ ext{Activity}}{ ext{Total Amount of Protein}} )

Protein Isolation Methods

Example 1: Purification of an Enzyme (e.g., Lactate Dehydrogenase)
  1. Disruption of Cells (Cell Lysis): Homogenization
  2. Centrifugation: Differential centrifugation for fractionation
  3. Enzyme Activity Assay: Monitor enzyme activity in each fraction (e.g., cytoplasm)
Differential Centrifugation
  • Salting Out: Proteins precipitate at high salt concentrations (different proteins at different salt molarities, e.g., ammonium sulfate).
  • Dialysis: Removal of small molecules like salt ions through a semipermeable membrane.
Column Chromatography Techniques
1. Molecular Exclusion/Gel Filtration Chromatography
  • Principle: Separation of protein molecules based on size and their ability to enter the pores of the gel.
2. Ion-Exchange Chromatography
  • Process: Bound molecules are eluted by increasing ionic strength (adding salt) or changing pH of the elution buffer.
  • Separation Based On: Charge properties and reversible binding to charged resin particles.
3. Affinity Chromatography
  • Process: Proteins are separated based on affinity for specific ligands and eluted by adding free ligands to the elution buffer.

Electrophoretic Analysis of Proteins

  • Proteins can be separated and identified via gel electrophoresis based on size (MW) and/or net charge (pI).
  • Electrophoresis Explained: The separation of charged molecules (DNA, Proteins) under electric field influence through gel pores.
Gel Electrophoresis Types
  1. Polyacrylamide Gel Electrophoresis (PAGE): Most common medium; acrylamide and bisacrylamide form the gel.
SDS-PAGE (Sodium Dodecyl Sulfate-PAGE)
  • Function: Accurately determines polypeptide size under denaturing conditions.
  • Operation: SDS disrupts protein structures, providing them with an overall negative charge, allowing their separation based only on size.
  • Reducing Agents: DTT or β-mercaptoethanol cleave disulfide bonds to separate protein subunits.
Electrophoretic Mobility
  • Relationship to MW: Electrophoretic mobility (Rf) is inversely proportional to the logarithm of the protein's MW.
  • Formula: ( Rf = \frac{x}{G} ) where x is the distance traveled by the protein, and G is the distance traveled by the front.
Isoelectric Focusing
  • Method: For separating proteins based on pI, proteins migrate through a gel with a pH gradient until they reach the point where their charge is neutral (pI).
Two-Dimensional Electrophoresis
  • Combination of Techniques: Allows for enhanced resolution in separating proteins, facilitating the analysis of expression levels and identification for diagnostic purposes.

Evaluation of Protein Purification

  1. Monitor qualitatively using SDS-PAGE.
  2. Monitor quantitatively using total protein, total activity, specific activity, yield, and purification level after each step.
Example 2: Purification of a Protein Without Enzymatic Activity (Estrogen Receptor)
  • Detection Method: Monitoring distinct binding properties (e.g., receptor-estradiol complex detection) using techniques like zonal centrifugation.

Antibody-Related Techniques

Antibody Production
  • Antibodies can be raised against specific antigens by injecting the protein or parts of it into animals and isolating their serum.
Monoclonal Antibodies
  • Created by fusing antibody-producing cells with cancer cells (e.g., multiple myeloma).
  • Clinical Uses: For detecting proteins and viruses and as therapeutic agents.

Immunological Techniques in Protein Analysis

Immunoprecipitation
  • A method where the target protein is “fished” out using a monoclonal antibody.
ELISA (Enzyme-Linked Immunosorbent Assay)
  • For detection and quantification of proteins.
  • Examples include HIV tests and pregnancy tests.
Western Blotting (Immunoblotting)
  • Process: Electrotransfer proteins to a membrane, followed by incubation with specific antibodies.
  • Used for diagnostic purposes, such as viral protein detection and identification of oligoclonal bands in cerebrospinal fluid for diagnosing multiple sclerosis.

Detection of Antigens

  • Methods include rapid tests (lateral flow tests, dipsticks) for various antigens such as those for COVID-19.

Determination of Amino Acid Sequence

Determination Techniques
  1. Amino Acid Composition: E.g., with Ala-Gly-Asp-Phe-Arg-Gly subjected to hydrolysis.
  2. Ion Exchange Chromatography: To separate amino acids based on charge, eluating with a pH gradient buffer.
  3. Edman Degradation: To determine the amino terminal residue, allowing the sequence for peptides up to 50 amino acids to be determined.
Protein Cleavage for Sequencing
  • Polypeptides can be cleaved at specific sites to facilitate sequencing; sequences can be determined through overlapping peptide analysis.
Mass Spectrometry (MS)
  • Allows for precise determination of protein mass, with techniques like MALDI-TOF facilitating identification based on peptide fingerprints.
Tandem Mass Spectrometry
  • For amino acid sequencing of peptides, enabling protein gene cloning through DNA sequence determination and translation according to the genetic code.
Importance of Amino Acid Sequence
  1. Identifies function, enabling comparison and classification of proteins.
  2. Allows evolutionary comparisons amongst species.
  3. Facilitates detection of mutations leading to disease at the molecular level.

Summary of Protein Analysis Methods

  • Techniques and methodologies detailed throughout ensure robust understanding and practical application in protein analysis critical in both research and clinical settings.

Revision Questions

  1. An enzyme that binds strongly to an ion exchange chromatography gel and elutes slowly:
    • A. has the same charge as the resin at the pH of the elution solution.
    • B. has a size larger than the gel pore size.
    • C. can be eluted by adding its substrate to the elution solution.
    • D. can be eluted by adding salt to the elution solution.
    • E. can be eluted by reducing the ionic strength of the elution solution.
  2. The Western immunoblotting method includes all the following except:
    • A. Electro-transfer on a membrane.
    • B. Labelling of an antibody with an enzyme.
    • C. Binding of an antibody to solid beads.
    • D. Protein analysis by SDS-PAGE.
    • E. Incubation of membrane with antibody.