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Understanding QSAR in Drug Design

Aug 31, 2024

Notes on QSAR (Quantitative Structure-Activity Relationship)

Introduction to QSAR

  • Definition: QSAR is a mathematical relationship between biological activity (dependent variable) and molecular descriptors (independent variables).
  • Key Components:
    • Dependent Variable: Activity (Y)
    • Independent Variables: Descriptors (X) related to geometric, physical, electronic, and chemical properties.

Types of Descriptors

  • Categories:
    • Geometric Descriptors: Shape, size.
    • Physical Descriptors: Volume, lipophilicity, solubility.
    • Electronic Descriptors: Charge, polarizability.
    • Chemical Properties: Hydrogen bonding capabilities.
  • Examples: Thousands of descriptors can be calculated for analysis.

Electronic Descriptors

  • Hammett Equation: Utilizes dissociation constants of substituted benzoic acids.
    • Dissociation Constant (K): Varies based on substituent position (ortho, meta, para) and type.
    • Electron-Withdrawing vs. Electron-Donating Groups:
      • Electron-withdrawing groups stabilize the anion form (high K).
      • Electron-donating groups stabilize the acid form (low K).

Importance of Electron Effects

  • Antibacterial Activity: Sulfa drugs mimic para-aminobenzoic acid (substrate for bacteria).
  • The active form is the anion, not the neutral form.
  • Activity influenced by substituent types (donating vs. withdrawing).

Acyclic and Hydrolysis Effects

  • Hydrolysis of Esters: Affected by nucleophilic attack on carbonyl carbon.
    • Effect of R Group Size: Larger R groups hinder nucleophilic attack, decreasing activity (Taft parameter).
  • Overall Activity Trends: Small R increases activity; larger R decreases it.

Log P (Partition Coefficient)

  • Definition: Log P = log ([octanol]/[water])
  • Indicates hydrophilicity/hydrophobicity.
    • Higher Log P = more hydrophobic; lower Log P = more hydrophilic.
  • Applications: Correlated with drug absorption, distribution, and activity.

Log P and Drug Activity

  • Anticonvulsant Activity: Relates to Log P; more hydrophobic compounds show increased activity.
  • Anesthetic Activity: Follows a parabolic relationship with Log P, indicating an optimal value around 2.3 for maximum activity.

Hammett and Taft Parameters

  • Hammett Substituent Constant (Sigma): Measures electron-withdrawing or donating influence.
  • Taft Steric Parameters: Measures steric effects in aliphatic systems (no resonance).
  • Calculation: Based on rates of hydrolysis under different conditions.

Comparative Analysis of Substituents

  • Crane Plot: Used for evaluating substituents based on hydrophobicity (pi) and electronic effects (sigma).
  • Orthogonality: Important for selecting substituents; ensures varied activity without correlation.

Toppan Scheme for QSAR Analysis

  • A systematic approach for synthesizing new molecules to maintain a balance of hydrophobic and electronic properties.
  • Selection Criteria: Substituents should provide a range of values for properties studied, ensuring orthogonality.

Conclusion

  • QSAR is a vital tool for drug design and development, leveraging statistical relationships to predict biological activity based on molecular structure.