Improved Binding Free Energy Predictions from Single-Reference Thermodynamic Integration Augmented with Hamiltonian Replica Exchange

Abstract

Reliable predictions of relative binding free energies are essential in drug discovery, where chemists modify promising compounds with the aim of increasing binding affinity. Conventional thermodynamic integration (TI) approaches can estimate corresponding changes in binding free energies but suffer from inadequate sampling due to the ruggedness of the molecular energy surfaces. Here, we present an improved TI strategy for computing relative binding free energies of congeneric ligands. This strategy employs a specific, unphysical single-reference (SR) state and Hamiltonian replica exchange (HREX) to locally enhance sampling. We then apply this strategy to compute relative binding free energies of 12 ligands in the L99A mutant of T4 lysozyme. Besides the ligands, our approach enhances hindered rotations of the important V111 as well as V87 and L118 side chains. Concurrently, we devise practical strategies to monitor and improve HREX-SRTI efficiency. Overall, the HREX-SRTI results agree well (R2 = 0.76,RMSE = 0.3 kcal/mol) with available experimental data.When optimized for efficiency, the HREX-SRTI precision matches that of experimental measurements.

Open PDF

Document Details

Document Type
Technical Report
Publication Date
Aug 15, 2011
Accession Number
ADA549734

Entities

People

  • Anders Wallqvist
  • Ilja V. Khavrutskii

Tags

Communities of Interest

  • Biomedical

DTIC Thesaurus Topics

  • Application Software
  • Biomedical Research
  • Cyclic Compounds
  • Efficiency
  • Energy
  • Experimental Data
  • Free Energy
  • Geometry
  • Molecular Dynamics
  • Molecular Mechanics Methods
  • Muramidase
  • Nanosecond Time
  • Precision
  • Rotation
  • Sampling
  • Simulations
  • Small Molecules

Readers

  • Molecular and Cellular Biochemistry
  • Oncology
  • Quantum Chemistry