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Accurate Free Energies for Complex Condensed-Phase Reactions Using an Artificial Neural Network Corrected DFTB/MM Methodology

Journal Article · · Journal of Chemical Theory and Computation
 [1];  [1];  [1];  [2];  [3];  [4];  [1];  [5]
  1. Karlsruhe Inst. of Technology (KIT) (Germany). Inst. of Physical Chemistry
  2. Univ. of Tennessee, Knoxville, TN (United States). Bredesen Center for Interdisciplinary Research and Graduate Education
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); US Department of Energy (USDOE), Washington DC (United States). National Virtual Biotechnology Lab.
  4. Heidelberg Institute for Theoretical Studies (Germany)
  5. Karlsruhe Inst. of Technology (KIT) (Germany). Inst. of Physical Chemistry; Karlsruhe Inst. of Technology (KIT) (Germany). Inst. of Biological Interfaces

Semiempirical methods like density functional tight-binding (DFTB) allow extensive phase space sampling, making it possible to generate free energy surfaces of complex reactions in condensed-phase environments. Such a high efficiency often comes at the cost of reduced accuracy, which may be improved by developing a specific reaction parametrization (SRP) for the particular molecular system. Thiol–disulfide exchange is a nucleophilic substitution reaction that occurs in a large class of proteins. Its proper description requires a high-level ab initio method, while DFT-GAA and hybrid functionals were shown to be inadequate, and so is DFTB due to its DFT-GGA descent. We develop an SRP for thiol–disulfide exchange based on an artificial neural network (ANN) implementation in the DFTB+ software and compare its performance to that of a standard SRP approach applied to DFTB. Furthermore, as an application, we use both new DFTB-SRP as components of a QM/MM scheme to investigate thiol–disulfide exchange in two molecular complexes: a solvated model system and a blood protein. Demonstrating the strengths of the methodology, highly accurate free energy surfaces are generated at a low cost, as the augmentation of DFTB with an ANN only adds a small computational overhead.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1863306
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 2 Vol. 18; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (52)

Theoretical Insights into the Mechanism for Thiol/Disulfide Exchange journal January 2004
Interplay of Chemical Microenvironment and Redox Environment on Thiol-Disulfide Exchange Kinetics journal July 2011
Nucleophilic Substitution (S N 2): Dependence on Nucleophile, Leaving Group, Central Atom, Substituents, and Solvent journal April 2018
Benchmarking density functional tight binding models for barrier heights and reaction energetics of organic molecules journal July 2017
Ligand‐induced transition in conformations of vicinal cysteine disulfides in proteins
  • Reddy, K. Kasi Amarnath; Jayashree, Muddagoni; Govindu, Panchada Ch V.
  • Proteins: Structure, Function, and Bioinformatics, Vol. 89, Issue 6 https://doi.org/10.1002/prot.26039
journal March 2021
Software update: the ORCA program system, version 4.0: Software update journal July 2017
The ORCA program system: The ORCA program system journal June 2011
Theoretical studies of enzymic reactions: Dielectric, electrostatic and steric stabilization of the carbonium ion in the reaction of lysozyme journal May 1976
A fifth-order perturbation comparison of electron correlation theories journal May 1989
PLUMED 2: New feathers for an old bird journal February 2014
GROMACS: High performance molecular simulations through multi-level parallelism from laptops to supercomputers journal September 2015
Machine Learning in QM/MM Molecular Dynamics Simulations of Condensed-Phase Systems journal April 2021
Development of Range-Corrected Deep Learning Potentials for Fast, Accurate Quantum Mechanical/Molecular Mechanical Simulations of Chemical Reactions in Solution journal October 2021
Machine-Learning-Assisted Free Energy Simulation of Solution-Phase and Enzyme Reactions journal September 2021
Big Data Meets Quantum Chemistry Approximations: The Δ-Machine Learning Approach journal April 2015
Is It Possible To Obtain Coupled Cluster Quality Energies at near Density Functional Theory Cost? Domain-Based Local Pair Natural Orbital Coupled Cluster vs Modern Density Functional Theory journal August 2015
Molecular Dynamics Simulations with Quantum Mechanics/Molecular Mechanics and Adaptive Neural Networks journal February 2018
Allosteric Disulfide Bonds journal June 2006
DFTB3: Extension of the Self-Consistent-Charge Density-Functional Tight-Binding Method (SCC-DFTB) journal March 2011
Parametrization and Benchmark of DFTB3 for Organic Molecules journal November 2012
Parameterization of DFTB3/3OB for Sulfur and Phosphorus for Chemical and Biological Applications journal March 2014
Benchmarking of Density Functionals for the Accurate Description of Thiol–Disulfide Exchange journal October 2014
Description of Phosphate Hydrolysis Reactions with the Self-Consistent-Charge Density-Functional-Tight-Binding (SCC-DFTB) Theory. 1. Parameterization journal November 2008
Comparisons of rate constants for thiolate-disulfide interchange in water and in polar aprotic solvents using dynamic proton NMR line shape analysis journal January 1990
Structure-reactivity correlations for the thiol-disulfide interchange reaction journal November 1977
Rate constants and equilibrium constants for thiol-disulfide interchange reactions involving oxidized glutathione journal March 1980
Mechanism of Thiolate−Disulfide Interchange Reactions in Biochemistry journal December 2007
DFTB+, a Sparse Matrix-Based Implementation of the DFTB Method journal July 2007
Are Current Semiempirical Methods Better Than Force Fields? A Study from the Thermodynamics Perspective journal July 2009
Potential Energy Surfaces Fitted by Artificial Neural Networks journal March 2010
Machine-learned potentials for next-generation matter simulations journal May 2021
The TensorMol-0.1 model chemistry: a neural network augmented with long-range physics journal January 2018
On the mechanism of spontaneous thiol–disulfide exchange in proteins journal January 2018
Electrostatic interactions contribute to the control of intramolecular thiol–disulfide isomerization in a protein journal January 2021
Machine learning of solvent effects on molecular spectra and reactions journal January 2021
Particle mesh Ewald: An N ⋅log( N ) method for Ewald sums in large systems journal June 1993
Neural network models of potential energy surfaces journal September 1995
Natural triple excitations in local coupled cluster calculations with pair natural orbitals journal October 2013
Perspective: Machine learning potentials for atomistic simulations journal November 2016
SchNet – A deep learning architecture for molecules and materials journal June 2018
DFTB+, a software package for efficient approximate density functional theory based atomistic simulations journal March 2020
A simplified charge projection scheme for long-range electrostatics in ab initio QM/MM calculations journal January 2021
Mechanistic insights on the reduction of glutathione disulfide by protein disulfide isomerase journal May 2017
Allosteric disulfides: Sophisticated molecular structures enabling flexible protein regulation journal January 2019
A new family of power transformations to improve normality or symmetry journal December 2000
Labile disulfide bonds are common at the leucocyte cell surface journal November 2011
Density functional tight binding
  • Elstner, Marcus; Seifert, Gotthard
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 372, Issue 2011 https://doi.org/10.1098/rsta.2012.0483
journal March 2014
Generalized Neural-Network Representation of High-Dimensional Potential-Energy Surfaces journal April 2007
Improving the learning speed of 2-layer neural networks by choosing initial values of the adaptive weights conference January 1990
Structure and dynamics of the platelet integrin-binding C4 domain of von Willebrand factor journal January 2019
Artificial neural network correction for density-functional tight-binding molecular dynamics simulations journal June 2019
Density-functional based tight-binding: an approximate DFT method journal January 2009

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