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Preparation details

The input files for the QligFEPv2 benchmarking experiments are all listed in the startFiles directory. Any modifications applied to the original structures obtained from the IndustryBenchmarks2024 repository (zenodo link) are described below.

  1. The notebook used to download the files from the IndustryBenchmarks2024 repository is available here.
  2. The ligand structure alignment mentioned in the manuscript is performed with the ligand alignment notebook.
  3. The notebook used to apply the standard Q-compatible atom namings to the pdb files and to run qprep to create the water spheres is available here.
  4. Finally, the creation of the perturbation networks is performed with the network creation notebook.

JACS Benchmark set;

The JACS benchmark set is a set of 8 protein-ligand systems used to benchmark the QligFEPv2 software. The prepared ligands/structures used for our calculations are the same reported in the IndustryBenchmark2024 repository, with exception of Thrombin, which was prepared by us.

Here you can find the modifications applied to each of the targets obtained from the original repository:

bace

All ligands and respective protein structure were loaded in Maestro. A minimization step was applied to the following residues by manually selecting them and minimizing with the Ctrl + m command: ILE171, SER96, SER71, PHE169, GLY291

cdk2

All ligands and respective protein structure were loaded in Maestro. A minimization step was applied to the following residues by manually selecting them and minimizing with the Ctrl + m command: LYS89, ASP86, LEU138

N-terminal of Chain A was also minimized to remove a clash leading to infinite VDW potentials.

Ligand Changes

An additional change was introduced to the input ligand structures. We noticed poorer correlation with the experimental data when using the ligands from the IndustryBenchmarks2024 repository. Ligand 17 in the series contains a halogen meta-substituted phenyl ring, pointing towards the solvent. The protein structure 6GUK, though different from the ligand in question, displays a different rotamer pointing towards the cyclohexyl group, less solvent-exposed. The space where the chlorine group is positioned in this deposited structure has an overlap of both 2Fo-Fc $\sigma$ and Fo-Fc(-ve) $\sigma$ maps, indicating an uncertainty in the positioning of the halogen atom. However, we assumed the rotamer conformation to have contributed for the poor correlation between QligFEP results with the experimental data and decided to use poses with the halogen pointing towards the cyclohexyl group.

jnk1

All ligands and respective protein structure were loaded in Maestro. A minimization step was applied to the following residues by manually selecting them and minimizing with the Ctrl + m command: GLY35, VAL40, LEU110, MET111, ALA113

mcl1

All ligands and respective protein structure were loaded in Maestro. A minimization step was applied to the following residues by manually selecting them and minimizing with the Ctrl + m command: VAL253, MET231, LEU246, LEU290, ILE294, LEU267, MET250, VAL274, LEU235, PHE270, GLY271

p38

No manual minimization performed. Bad clashes were only observed against water molecules, which are automatically removed before QligFEP RBFE simulations.

ptp1b

Prepared protein from the source repository displayed poor correlation with the experimental data. Therefore, we proceeded to use an internally prepared structure by us, generated before this study was conducted and known to work well with QligFEP RBFE calculations.

Upon checking the ligands, we noticed a need for optimization of the ligand poses. Despite the good MCS alignment for the scaffold shared by the ligands, other parts of the ligand weren't so well aligned. Therefore, we decided to perform a few additional alignments on top of the ligand preparation on IndustryBenchmarks2024 repository. The changes can be found in our ligand alignment notebook.

thrombin

The protein found in the source repository contained some hydrogen positioning problems, which we attempted to fix using Maestro's Refine > H-bond-assignment tool. Further, some amino acids were placed in the sequence in the incorrect order. Those were fixed by manually reordering them.

The resulting structure, however, resulted in crashes during the FEP, which wasn't observed for any of the other targets used in this study. Therefore, we proceeded to use an internally prepared structures by us.

tyk2

All ligands and respective protein structure were loaded in Maestro. A minimization step was applied to the following residues by manually selecting them and minimizing with the Ctrl + m command: LEU903, TYR980, GLY984, PRO982

Merck Benchmark set;

cdk8

All ligands and respective protein structure were loaded in Maestro. A minimization step was applied to the following residues by manually selecting them and minimizing with the Ctrl + m command: val27, gly28, tyr32, lys52, ile79, his102, asp103, asn156, leu158, arg356

cmet

All ligands and respective protein structure were loaded in Maestro. A minimization step was applied to the following residues by manually selecting them and minimizing with the Ctrl + m command: ile1084, gly1085, met1160, lys1161

eg5

All ligands and respective protein structure were loaded in Maestro. A minimization step was applied to the following residues by manually selecting them and minimizing with the Ctrl + m command: arg119, pro121, leu160, gly217, ala218

hif2a

met289, his293, cys339

pfkfb3

Ligands 20, 41, and 42 and respective protein structure were loaded in Maestro. A minimization step was applied to the following residues by manually selecting them and minimizing with the Ctrl + m command: val214

Following that, ligands 44, 47, 52, 53 were loaded. A second minimization step was applied to the folliwng residues by manually selecting them and minimizing with the Ctrl + m command: leu238, ile241, his242

The following water molecules were removed: 905, 914, 944, 993, 998, 1022, as they were clashing with other HOH O atoms and not the closest to the protein residues.

Removed the atoms:

ATOM      1  CH3 ACE A   0      87.427  98.432 260.536  1.00  0.00           C  
ATOM      2  C   ACE A   0      86.302  98.808 261.499  1.00  0.00           C  
ATOM      3  O   ACE A   0      85.472  97.963 261.827  1.00  0.00           O  
ATOM      4 1H   ACE A   0      87.325  97.362 260.246  1.00  0.00           H  
ATOM      5 2H   ACE A   0      87.370  99.072 259.627  1.00  0.00           H  
ATOM      6 3H   ACE A   0      88.411  98.593 261.030  1.00  0.00           H  
...
ATOM    284  N   NME A  16A     79.441  97.537 254.883  1.00  0.00           N  
ATOM    285  CA  NME A  16A     80.445  98.441 254.341  1.00  0.00           C  
ATOM    286  H   NME A  16A     78.820  97.041 254.262  1.00  0.00           H  
ATOM    287 1HA  NME A  16A     81.022  98.883 255.184  1.00  0.00           H  
ATOM    288 2HA  NME A  16A     81.132  97.880 253.668  1.00  0.00           H  
ATOM    289 3HA  NME A  16A     79.949  99.249 253.759  1.00  0.00           H  

Ligand Changes

An additional change was introduced to the input ligand structures. We noticed poorer correlation with the experimental data for the edges including ligand 43 from the IndustryBenchmarks2024 repository. This ligand in the series contains a halogen (Br) meta-substituted phenyl ring, pointing towards the solvent. The protein structure 6HVI with the co-crystalized ligand 38 of the congeneric series also contains a meta-substitution of the phenyl ring, but on the opposite orientation than ligand 43. Therefore, we decided to flip the cyclohexyl group in ligand 43 to match the observed orientation in the protein structure. Doing so, we observed a better correlation between the calculated and experimental data, supporting the decision to use this pose.

shp2

phe113, his114, thr219, glu249, asp489, lys492

syk

The following residues were minimized to better accommodate the ligands in the binding site: glu376, leu377, gly378, val385, asn457, asp512, phe513, lys402, gly454, ser379, lys375, phe382, lys458

Further, other amino acids were minimized to avoid protein-protein clashes.

Finally, the orientation of the protein's hydrogen atoms were refined using Maestro's Refine > H-bond-assignment tool by checking the boxes:

  • Sample water orientations
  • Use PROPKA pH: 7.0

tnks2

No manual minimization performed.