Table 4. Interaction Affinity of Ergotamine (Unprotonated (ETA) and Singly Protonated (ETA+) States) to Monomers, Polymer Chains (10 U), and Large Polymeric Material Used in the Production of Imprinted Polymers Compared to the Formulation Used in This Study by Means of Molecular Mechanics.
| docking
affinity (kcal/mol)a |
||||||
|---|---|---|---|---|---|---|
| ETA |
ETA+ |
|||||
| monomer unit | abbr. | free energyb (kJ/mol) | best | average | best | average |
| ethoxyhydroxymandelic acid | EHMA | 58.9 | –5.6 | –5.4 ± 0.1 | –4.3 | –4.0 ± 0.1 |
| 1-2-vinyl benzene | VB | 39.2 | –5.3 | –5.0 ± 0.3 | –5.2 | –4.8 ± 0.2 |
| 4-vinyl benzoic acid | VBA | 23.0 | –5.3 | –4.8 ± 0.2 | –5.3 | –4.9 ± 0.2 |
| methylmethacrylate | MMA | 89.9 | –5.3 | –5.0 ± 0.1 | –1.8 | –1.6 ± 0.1 |
| trifluoromethylacrylic acid | TFMAA | –44.1 | –5.3 | –4.7 ± 0.2 | –5.3 | –4.9 ± 0.1 |
| 1-3-vinyl benzene | VB | 19.9 | –4.9 | –4.4 ± 0.3 | –4.8 | –4.2 ± 0.3 |
| methylhydroxymethacrylate | MHMA | 76.0 | –4.8 | –4.5 ± 0.1 | –4.7 | –4.3 ± 0.2 |
| 1-4-vinyl benzene | VB | 19.9 | –4.7 | –4.5 ± 0.1 | –4.5 | –4.3 ± 0.2 |
| styrene | STY | 18.1 | –4.6 | –4.2 ± 0.1 | –4.6 | –4.2 ± 0.2 |
| dimethylacrylamide | DMA | –24.9 | –3.9 | –3.4 ± 0.1 | –2.9 | –2.7 ± 0.1 |
| 4-vinyl pyridine | VP | 14.2 | –3.8 | –3.6 ± 0.1 | –4.1 | –3.8 ± 0.1 |
| 2-vinyl pyridine | VP | 17.0 | –3.7 | –3.4 ± 0.1 | –3.6 | –3.4 ± 0.1 |
| pentaerythrityl triacrylate | PETA | 36.4 | –3.7 | –3.5 ± 0.1 | –2.9 | –2.7 ± 0.1 |
| trimethylolpropane trimethacrylate | TMPTMA | 17.0 | –3.5 | –3.0 ± 0.2 | –3.5 | –3.1 ± 0.1 |
| 2-acrylamido-2-methyl-1-propane sulfonic acid | AMPSA | –58.2 | –3.4 | –3.0 ± 0.2 | –2.6 | –2.3 ± 0.1 |
| ethylene glycol dimethacrylate | EGDMA | 13.3 | –3.1 | –2.7 ± 0.1 | –3.3 | –2.9 ± 0.2 |
| hydroxyethyl methacrylate | HEMA | 7.4 | –2.8 | –2.6 ± 0.1 | –2.8 | –2.5 ± 0.1 |
| propyl acrylate | PA | –23.8 | –2.7 | –2.5 ± 0.1 | –2.8 | –2.6 ± 0.1 |
| dimethylaminoethyl methacrylate | DMAEM | 15.9 | –2.0 | –1.8 ± 0.0 | –2.6 | –2.3 ± 0.1 |
| methylmethacrylate | MMA | –14.5 | –1.9 | –1.7 ± 0.1 | –1.8 | –1.6 ± 0.1 |
| vinyl pyrrolidone | VPone | –28.9 | –1.9 | –1.7 ± 0.0 | –1.8 | –1.6 ± 0.0 |
| methacrylamide | MA | –29.5 | –1.8 | –1.6 ± 0.1 | –3.0 | –2.8 ± 0.0 |
| methyl acrylate | MA | –21.2 | –1.8 | –1.5 ± 0.1 | –1.7 | –1.5 ± 0.0 |
| acrylic acid | AA | –33.3 | –1.7 | –1.5 ± 0.0 | –1.7 | –1.6 ± 0.0 |
| 1-vinyl imidazole | VI | 210.5 | –1.6 | –1.4 ± 0.1 | –1.6 | –1.4 ± 0.1 |
| acrylamide | A | –29.2 | –1.4 | –1.3 ± 0.1 | –1.7 | –1.5 ± 0.0 |
| propylene | PP | –4.9 | –1.2 | –1.1 ± 0.0 | –1.2 | –1.1 ± 0.0 |
| vinyl alcohol | VA | –1.5 | –1.2 | –1.1 ± 0.0 | –1.2 | –1.0 ± 0.1 |
| vinyl fluoride | VF | –2.4 | –1.2 | –1.0 ± 0.0 | –1.1 | –1.0 ± 0.0 |
| polymer chain | ||||||
| MIP polymer: styrene-methylmethacrylate, 100 Åc | -[PMMA-PS-PMA-PMAA]n | –11.7 | –10.8 ± 0.3 | –11.1 | –9.9 ± 0.5 | |
| NIP polymer: styrene-methylmethacrylate, 100 Åd | -[PMMA-PS-PMA-PMAA]n | –10.4 | –9.6 ± 0.4 | –10.0 | –9.6 ± 0.2 | |
| MIP/NIP Chain, 10 U (Units) | -[EGDMA2-STY2-HEMA]2 | 188.9 | –9.2 | –8.5 ± 0.3 | –9.3 | –8.6 ± 0.3 |
| polystyrene (atactic), 10 U | aPSYN10 | 2057.0 | –8.6 | –8.0 ± 0.2 | –8.6 | –7.9 ± 0.3 |
| polypropyl acrylate (atactic), 10 U | aPPA10 | –124.1 | –7.2 | –6.6 ± 0.2 | –7.2 | –6.5 ± 0.3 |
| polystyrene (syndio), 10 U | sPSTY | 238.9 | –6.5 | –6.3 ± 0.1 | –6.2 | –6.1 ± 0.1 |
| polymethyl methacrylate (atactic), 10 U | aPMMA10 | 121.2 | –6.3 | –5.8 ± 0.3 | –6.3 | –5.8 ± 0.3 |
| polymethyl methacrylate (syndio) | sMMA | 123.5 | –6.1 | –5.7 ± 0.1 | –6.0 | –5.7 ± 0.1 |
| polymethylacrylate (atactic), 10 U | aPMA10 | –86.2 | –5.8 | –5.4 ± 0.2 | –5.8 | –5.5 ± 0.2 |
| polyvinyl pyrrolidone (atactic), 10 U | aPVP10 | 198.1 | –5.6 | –5.2 ± 0.2 | –5.8 | –5.2 ± 0.3 |
| polyhydroxyethyl methacrylate (atactic), 10 U | aPHEMA | 151.2 | –5.6 | –5.3 ± 0.1 | –5.2 | –4.6 ± 0.2 |
| polypropylene (atactic), 10 U | aPPE10 | 74.6 | –5.3 | –5.1 ± 0.1 | –5.4 | –5.1 ± 0.1 |
| polymethylmethacrylate (isotactic), 10 U | iPMMA | 123.4 | –5.1 | –4.7 ± 0.2 | –5.1 | –4.7 ± 0.2 |
| polyacrylic acid (atactic), 10 U | aPAA10 | –260.4 | –4.8 | –4.4 ± 0.2 | –4.7 | –4.3 ± 0.2 |
| polyvinyl fluoride (atactic), 10 U | aPVF10 | –34.2 | –4.6 | –4.3 ± 0.2 | –4.7 | –4.3 ± 0.2 |
| polyvinyl alcohol (atactic), 10 U | aPVA10 | 50.2 | –3.9 | –3.7 ± 0.1 | –4.0 | –3.8 ± 0.0 |
| polyamide (atactic), 10 U | aPA10 | –133.0 | –2.6 | –2.4 ± 0.0 | –2.8 | –2.7 ± 0.0 |
a
Docking experiments and affinity measurements were performed with AutoDock Vina.
b
Minimization of all other monomers and ETA was performed under MMFF94 force field after 100,000 minimization iterations.
c
MIP built and equilibrated at 338 K (CHARMM-GUI, CHARMM36 all atom force field) by dynamic simulation in a toluene cubical solvent box of 100 Å side length with a volumic ratio of 87.7% corresponding to the MIP occupancy compared to NIP using pore diameter information (Table 1).
d
NIP built and equilibrated at 338 K (CHARMM-GUI) by dynamic simulation in a toluene cubical solvent box of 100 Å side length with a volumic ratio of 100% corresponding to the NIP occupancy.