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Lambda-ABF-OPES: Faster Convergence with High Accuracy in Alchemical Free Energy Calculations

Published 24 Feb 2025 in physics.chem-ph and q-bio.BM | (2502.17233v2)

Abstract: Predicting the binding affinity between small molecules and target macromolecules while combining both speed and accuracy, is a cornerstone of modern computational drug discovery which is critical for accelerating therapeutic development. Despite recent progresses in molecular dynamics (MD) simulations, such as advanced polarizable force fields and enhanced-sampling techniques, estimating absolute binding free energies (ABFE) remains computationally challenging. To overcome these difficulties, we introduce a highly efficient, hybrid methodology that couples the Lambda-Adaptive Biasing Force (Lambda-ABF) scheme with On-the-fly Probability Enhanced Sampling (OPES). This approach achieves up to a nine-fold improvement in sampling efficiency and computational speed compared to the original Lambda-ABF when used in conjunction with the AMOEBA polarizable force field, yielding converged results at a fraction of the cost of standard techniques.

Summary

Lambda-ABF-OPES: Enhancing Efficiency and Accuracy in Alchemical Free Energy Calculations

The paper presents a significant advancement in the field of computational drug discovery through the introduction of a hybrid methodology termed Lambda-ABF-OPES. This method integrates the Lambda-Adaptive Biasing Force (Lambda-ABF) with the On-the-fly Probability Enhanced Sampling (OPES) framework, aiming to improve the efficiency of alchemical free energy calculations.

Methodological Approach

The study acknowledges the pivotal role of predicting binding affinities in drug development, a task often confronted by challenges such as computational expenses and sampling efficiency. Traditional methods, while effective, face hurdles due to the complexity of molecular interactions and the configurational space they must explore. To address these, the authors propose an innovative combination of Lambda-ABF and OPES, leveraging the strengths of both approaches.

Lambda-ABF has shown effectiveness in enhancing the sampling of ‘lambda’ as a collective variable by applying adaptive biasing forces based on the thermodynamic integration formula. OPES, on the other hand, belongs to the MetaDynamics family and broadens the sampling by constructing a bias potential, aiding the system’s exploration. The hybrid method applies OPES to the lambda CV in Lambda-ABF, resulting in a more efficient exploration of the configurational landscape and overcoming kinetic barriers.

Numerical Results

A benchmark application of the method was performed on 11 drug-like molecules binding to the bromodomain BRD4. Using the AMOEBA polarizable force field and DBC restraints, the approach demonstrated a reduction in sampling time by up to nine times compared to Lambda-ABF alone, without compromising on the accuracy of the computed binding affinities. The correlation between computational predictions and experimental data was robust, with a mean absolute error of 0.90 kcal/mol.

Practical and Theoretical Implications

The development of the Lambda-ABF-OPES method provides a valuable tool for computational chemistry, specifically in drug discovery. Practically, the reduction in computational cost and time implies that larger chemical spaces can be explored in less time, which is crucial for high-throughput screening processes. Theoretically, this integration sets a precedent for hybrid approaches in enhanced sampling methods, showing how combining methodologies can address specific drawbacks while retaining their strengths.

The authors suggest broad applicability within enhanced sampling techniques, and there is anticipation that this method could be adapted or extended to other advanced potential energy models, including machine learning interatomic potentials (MLIPs) and neural network-based methods. Such extensions could further revolutionize accuracy and efficiency not only in drug discovery but potentially in materials science and other domains reliant on molecular simulations.

Future Directions

The future direction hinted by the authors involves broadening the scope of Lambda-ABF-OPES in various computational fields, integrating it with neural networks, and further developing its theoretical underpinnings. The potential for applying this methodology to diverse molecular systems, combined with its adaptable nature for improving convergence and efficiency, marks it as a promising avenue for future research.

In summary, the paper provides an insightful contribution to computational methods in chemistry, offering a nuanced approach that balances efficiency and accuracy, potentially influencing a wide range of applications beyond its current scope.

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