Systematic Parameterization of Ion–Surfactant Interactions in Dissipative Particle Dynamics Using Setschenow Coefficients

Abstract

Dissipative particle dynamics (DPD) simulations of nonionic surfactants with an added salt show that the Setschenow relationship is reproduced; that is, the critical micelle concentration is log-linearly dependent on the added salt concentration. The simulated Setschenow coefficients depend on the DPD bead–bead repulsion amplitudes, and matching to the experimentally determined values provides a systematic method to parameterize the interactions between salt ion beads and surfactant beads. The optimized ion-specific interaction parameters appear to be transferrable and follow the same trends as the empirical Hofmeister series.

Structure–Stability Relationship in Aqueous Colloids of Latex Particles and Gemini Surfactants

“…Comparing the charge density and CCIS values in the presence of KCl and CaCl 2 , the higher affinity of the Ca 2+ to the negatively charged particle is clearly visible since these parameters decreased significantly as the counterion’s valence was increased. This finding can be explained by the fact that divalent cations are more effective in charge screening than monovalent ones, as reported earlier in other particle–electrolyte systems. ,,− …”

“…This finding can be explained by the fact that divalent cations are more effective in charge screening than monovalent ones, as reported earlier in other particle–electrolyte systems. 11 , 18 , 53 − 56 …”

Structure–Stability Relationship in Aqueous Colloids of Latex Particles and Gemini Surfactants

“…Comparing the charge density and CCIS values in the presence of KCl and CaCl 2 , the higher affinity of the Ca 2+ to the negatively charged particle is clearly visible since these parameters decreased significantly as the counterion’s valence was increased. This finding can be explained by the fact that divalent cations are more effective in charge screening than monovalent ones, as reported earlier in other particle–electrolyte systems. ,,− …”

“…This finding can be explained by the fact that divalent cations are more effective in charge screening than monovalent ones, as reported earlier in other particle–electrolyte systems. 11 , 18 , 53 − 56 …”

Hydrophobic Solute Encapsulation by Amphiphilic Mikto-Grafted Bottlebrushes: A Dissipative Particle Dynamics Study

“…By using the relationship provided by Groot and Warren, the DPD interaction parameters, a ij , between beads were calculated by using the Flory–Huggins parameters reported in the diverse literature studies. − However, we were unable to find data for PGMA, thus, we assumed that PLA and PGMA are identical in the model and represented these two molecules by the same interaction parameters. Notice that there have been recent attempts to parametrize DPD interactions to achieve a quantitative agreement with experimental data, − and the results from these efforts are very encouraging; in here, however, we focus on a qualitative comparison with experimental phenomenology rather than a precise quantitative comparison. Table lists the Flory–Huggins parameters for all different molecules simulated in this work; as can be seen in the table, the Flory–Huggins parameter associated with the pair PEG-PLA is negative, indicating that these two polymers are compatible.…”

A Coarse-Grained Model Describing the Critical Micelle Concentration of Perfluoroalkyl Surfactants in Ionic Aqueous Phase

“…This distributes charge smoothly over beads, avoiding issues with point charges like infinite potential and unrealistic ion pairs. 36,38,43,50,51 We employed the formulation of Gonzaĺez-Melchor et al 38 for the smeared electrostatic force. All of the simulation parameters and the conversion table to real units are available in Section S1.1 of the Supporting Information.…”

“…The bead types reflected hydrophobicity and charge, and their volumes were determined using the Materials Studio QSAR Models module 54 (see Table S2 Subsequently, we optimized the repulsion between the tail beads and the water beads, as this interaction plays a crucial role in driving hydrophobicity and significantly affects the CMC of the surfactant. 12,29,36,55 Sections S3 and S4 in the Supporting Information provide comprehensive lists of all the parameters used. The parameters provided in this work are surfactant independent, and they are consistent for all molecules sharing the same functional group.…”

Structure–Stability Relationship in Aqueous Colloids of Latex Particles and Gemini Surfactants

“…Comparing the charge density and CCIS values in the presence of KCl and CaCl 2 , the higher affinity of the Ca 2+ to the negatively charged particle is clearly visible since these parameters decreased significantly as the counterion’s valence was increased. This finding can be explained by the fact that divalent cations are more effective in charge screening than monovalent ones, as reported earlier in other particle–electrolyte systems. ,,− …”

“…This finding can be explained by the fact that divalent cations are more effective in charge screening than monovalent ones, as reported earlier in other particle–electrolyte systems. 11 , 18 , 53 − 56 …”

Hydrophobic Solute Encapsulation by Amphiphilic Mikto-Grafted Bottlebrushes: A Dissipative Particle Dynamics Study

“…By using the relationship provided by Groot and Warren, the DPD interaction parameters, a ij , between beads were calculated by using the Flory–Huggins parameters reported in the diverse literature studies. − However, we were unable to find data for PGMA, thus, we assumed that PLA and PGMA are identical in the model and represented these two molecules by the same interaction parameters. Notice that there have been recent attempts to parametrize DPD interactions to achieve a quantitative agreement with experimental data, − and the results from these efforts are very encouraging; in here, however, we focus on a qualitative comparison with experimental phenomenology rather than a precise quantitative comparison. Table lists the Flory–Huggins parameters for all different molecules simulated in this work; as can be seen in the table, the Flory–Huggins parameter associated with the pair PEG-PLA is negative, indicating that these two polymers are compatible.…”

A Coarse-Grained Model Describing the Critical Micelle Concentration of Perfluoroalkyl Surfactants in Ionic Aqueous Phase

“…This distributes charge smoothly over beads, avoiding issues with point charges like infinite potential and unrealistic ion pairs. 36,38,43,50,51 We employed the formulation of Gonzaĺez-Melchor et al 38 for the smeared electrostatic force. All of the simulation parameters and the conversion table to real units are available in Section S1.1 of the Supporting Information.…”

“…The bead types reflected hydrophobicity and charge, and their volumes were determined using the Materials Studio QSAR Models module 54 (see Table S2 Subsequently, we optimized the repulsion between the tail beads and the water beads, as this interaction plays a crucial role in driving hydrophobicity and significantly affects the CMC of the surfactant. 12,29,36,55 Sections S3 and S4 in the Supporting Information provide comprehensive lists of all the parameters used. The parameters provided in this work are surfactant independent, and they are consistent for all molecules sharing the same functional group.…”

Structure–Stability Relationship in Aqueous Colloids of Latex Particles and Gemini Surfactants

“…Comparing the charge density and CCIS values in the presence of KCl and CaCl 2 , the higher affinity of the Ca 2+ to the negatively charged particle is clearly visible since these parameters decreased significantly as the counterion’s valence was increased. This finding can be explained by the fact that divalent cations are more effective in charge screening than monovalent ones, as reported earlier in other particle–electrolyte systems. ,,− …”

“…This finding can be explained by the fact that divalent cations are more effective in charge screening than monovalent ones, as reported earlier in other particle–electrolyte systems. 11 , 18 , 53 − 56 …”

Hydrophobic Solute Encapsulation by Amphiphilic Mikto-Grafted Bottlebrushes: A Dissipative Particle Dynamics Study

“…By using the relationship provided by Groot and Warren, the DPD interaction parameters, a ij , between beads were calculated by using the Flory–Huggins parameters reported in the diverse literature studies. − However, we were unable to find data for PGMA, thus, we assumed that PLA and PGMA are identical in the model and represented these two molecules by the same interaction parameters. Notice that there have been recent attempts to parametrize DPD interactions to achieve a quantitative agreement with experimental data, − and the results from these efforts are very encouraging; in here, however, we focus on a qualitative comparison with experimental phenomenology rather than a precise quantitative comparison. Table lists the Flory–Huggins parameters for all different molecules simulated in this work; as can be seen in the table, the Flory–Huggins parameter associated with the pair PEG-PLA is negative, indicating that these two polymers are compatible.…”

A Coarse-Grained Model Describing the Critical Micelle Concentration of Perfluoroalkyl Surfactants in Ionic Aqueous Phase

“…This distributes charge smoothly over beads, avoiding issues with point charges like infinite potential and unrealistic ion pairs. 36,38,43,50,51 We employed the formulation of Gonzaĺez-Melchor et al 38 for the smeared electrostatic force. All of the simulation parameters and the conversion table to real units are available in Section S1.1 of the Supporting Information.…”

“…The bead types reflected hydrophobicity and charge, and their volumes were determined using the Materials Studio QSAR Models module 54 (see Table S2 Subsequently, we optimized the repulsion between the tail beads and the water beads, as this interaction plays a crucial role in driving hydrophobicity and significantly affects the CMC of the surfactant. 12,29,36,55 Sections S3 and S4 in the Supporting Information provide comprehensive lists of all the parameters used. The parameters provided in this work are surfactant independent, and they are consistent for all molecules sharing the same functional group.…”