Free Energy Change of Micelle Formation for Sodium Dodecyl Sulfate from a Dispersed State in Solution to Complete Micelles along Its Aggregation Pathways Evaluated by Chemical Species Model Combined with Molecular Dynamics Calculations

作     者：YOSHII Noriyuki KOMORI Mika KAWADA Shinji TAKABAYASHI Hiroaki FUJIMOTO Kazushi OKAZAKI Susumu YOSHII Noriyuki;KOMORI Mika;KAWADA Shinji;TAKABAYASHI Hiroaki;FUJIMOTO Kazushi;OKAZAKI Susumu

作者机构：Center for Computational ScienceGraduate School of EngineeringNagoya UniversityNagoya 464-8603Japan Department of Applied ChemistryNagoya UniversityNagoya 464-8603Japan 

出 版 物：《物理化学学报》 (Acta Physico-Chimica Sinica)

年 卷 期：2018年第34卷第10期

页      面：1163-1170页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 0702[理学-物理学] 

基　　金：This work was supported by FLAGSHIP2020 MEXT within Priority Study 5(Development of New Fundamental Technologies for High-Efficiency Energy Creation Conversion/Storage and Use)Using Computational Resources of the K Computer Provided by the RIKEN Advanced 

主　　题：Free energy change Aggregation pathway SDS Micelle Molecular dynamics calculation 

摘      要：Surfactant molecules, when dispersed in solution, have been shown to spontaneously form aggregates. Our previous studies on molecular dynamics(MD) calculations have shown that ionic sodium dodecyl sulfate molecules quickly aggregated even when the aggregation number is small. The aggregation rate, however, decreased for larger aggregation numbers. In addition, studies have shown that micelle formation was not completed even after a 100 ns-long MD run(Chem. Phys. Lett. 2016, 646, 36). Herein, we analyze the free energy change of micelle formation based on chemical species model combined with molecular dynamics calculations. First, the free energy landscape of the aggregation, ?G_(i+j)^+, where two aggregates with sizes i and j associate to form the(i + j)-mer, was investigated using the free energy of micelle formation of the i-mer, G_i^+, which was obtained through MD calculations. The calculated ?G_(i+j)^+ was negative for all the aggregations where the sum of DS ions in the two aggregates was 60 or less. From the viewpoint of chemical equilibrium, aggregation to the stable micelle is desired. Further, the free energy profile along possible aggregation pathways was investigated, starting from small aggregates and ending with the complete thermodynamically stable micelles in solution. The free energy profiles, G(l, k), of the aggregates at l-th aggregation path and k-th state were evaluated by the formation free energy ∑_in_i( l,k)G_i^+ and the free energy of mixing ∑_in_i( l,k)k_BTln( n_i( l,k)/n( l,k)), where ni(l, k) is the number of i-mer in the system at the l-th i aggregation path and k-th state, with n(l,k)= ∑_n_i( l,k). All the aggregation pathways were obtained from the initial i state of 12 pentamers to the stable micelle with i = 60. All the calculated G(l, k) values monotonically decreased with increasing k. This indicates that there are no free energy barriers along the pathways. Hence, the slowdown is not due to the thermodynamic stability of the aggre