Citation: YOSHII Noriyuki, KOMORI Mika, KAWADA Shinji, TAKABAYASHI Hiroaki, FUJIMOTO Kazushi, OKAZAKI Susumu. 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[J]. Acta Physico-Chimica Sinica, ;2018, 34(10): 1163-1170. doi: 10.3866/PKU.WHXB201802271 shu

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

1.
Center for Computational Science, Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan
2.
Department of Applied Chemistry, Nagoya University, Nagoya 464-8603, Japan

Corresponding author: YOSHII Noriyuki, yoshii@ccs.engg.nagoya-u.ac.jp OKAZAKI Susumu, okazaki@apchem.nagoya-u.ac.jp
Received Date: 25 December 2017
Revised Date: 2 February 2018
Accepted Date: 19 February 2018
Available Online: 27 October 2018
Fund Project: 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 Institute for Computational Science through the HPCI System Research Project (hp170241). This work was also funded by MEXT KAKENHI Grant Number 17K04758 (N.Y.)

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, ΔG_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 ΔG_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 \begin{document}$\sum\limits_i {{n_i}\left( {l, k} \right)G_i^\dagger } $\end{document} and the free energy of mixing \begin{document}$\sum\limits_i {{n_i}(l, k){k_B}Tln({n_i}(l, k)/n(l, k))} $\end{document}, where n_i(l, k) is the number of i-mer in the system at the l-th aggregation path and k-th state, with \begin{document}$n\left( {l, k} \right) = \sum\limits_i {{n_i}\left( {l, k} \right)} $\end{document}. All the aggregation pathways were obtained from the initial 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 aggregates, but rather the kinetics that inhibit the association of the fragments. The time required for a collision between aggregates, one of the kinetic factors, was evaluated using the fast passage time, t_FPT. The calculated t_FPT was about 20 ns for the aggregates with N = 31. Therefore, if aggregation is a diffusion-controlled process, it should be completed within the 100 ns-simulation. However, aggregation does not occur due to the free energy barrier between the aggregates, that is, the repulsive force acting on them. This may be caused by electrostatic repulsions produced by the overlap of the electric double layers, which are formed by the negative charge of the hydrophilic groups and counter sodium ions on the surface of the aggregates.
- Free energy change,
- Aggregation pathway,
- SDS,
- Micelle,
- Molecular dynamics calculation
1. [1]
  Tanford, C. J. Phys. Chem. 1974, 78, 2469. doi: 10.1021/j100617a012 doi: 10.1021/j100617a012
2. [2]
  Israelachvili, J. N. Intermolecular and Surface Forces, 2nd ed. ; Academic Press: London, UK, 1992.
3. [3]
  Everett, D. H. Basic Principles of Colloid Science; The Royal Society of Chemistry: London, UK, 1988.
4. [4]
  Puvvada, S.; Blankschtein, D. J. Chem. Phys. 1990, 92, 3710. doi: 10.1063/1.457829 doi: 10.1063/1.457829
5. [5]
  Christopher, P. S.; Oxtoby, D. W. J. Chem. Phys. 2003, 118, 5665. doi: 10.1063/1.1554394 doi: 10.1063/1.1554394
6. [6]
  Maibaum, L.; Dinner, A. R.; Chandler, D. J. Phys. Chem. B 2004, 108, 6778. doi: 10.1021/jp037487t doi: 10.1021/jp037487t
7. [7]
  Yoshii, N.; Iwahashi, K.; Okazaki, S. J. Chem. Phys. 2006, 124, 184901. doi: 10.1063/1.2179074 doi: 10.1063/1.2179074
8. [8]
  Pool, R.; Bolhuis, P. G. J. Chem. Phys. 2007, 126, 244703. doi: 10.1063/1.2741513 doi: 10.1063/1.2741513
9. [9]
  Burov, S. V.; Shchekin, A. K. J. Chem. Phys. 2010, 133, 244109. doi: 10.1063/1.3519815 doi: 10.1063/1.3519815
10. [10]
  Verde, A. V.; Frenkel, D. Soft Matter 2010, 6, 3815. doi: 10.1039/C0SM00011F doi: 10.1039/C0SM00011F
11. [11]
  Bernardino, K.; de Moura, A. F. J. Phys. Chem. B 2013, 117, 7324. doi: 10.1021/jp312840y doi: 10.1021/jp312840y
12. [12]
  Marrink, S. J.; Tieleman, D. P.; Mark, A. E. J. Phys. Chem. B 2000, 104, 12165. doi: 10.1021/jp001898h doi: 10.1021/jp001898h
13. [13]
  Lazaridis, T.; Mallik, B.; Chen, Y. J. Phys. Chem. B 2005, 109, 15098. doi: 10.1021/jp0516801 doi: 10.1021/jp0516801
14. [14]
  Tieleman, D. P.; van der Spoel, D.; Berendsen, H. J. C. J. Phys. Chem. B 2000, 104, 6380. doi: 10.1021/jp001268f doi: 10.1021/jp001268f
15. [15]
  Bond, P. J.; Cuthbertson, J. M.; Deol, S. S.; Sansom, M. S. P. J. Am. Chem. Soc. 2004, 126, 15948. doi: 10.1021/ja044819e doi: 10.1021/ja044819e
16. [16]
  Jusufi, A.; Hynninen, A. -P.; Panagiotopoulos, A. Z. J. Phys. Chem. B 2008, 112, 13783. doi: 10.1021/jp8043225 doi: 10.1021/jp8043225
17. [17]
  Sanders, S.; Sammalkorpi, M.; Panagiotopoulos, A. Z. J. Phys. Chem. B 2012, 116, 2430. doi: 10.1021/jp209207p doi: 10.1021/jp209207p
18. [18]
  Sammalkorpi, M.; Karttunen, M.; Haataja, M. J. Phys. Chem. B 2007, 111, 11722. doi: 10.1021/jp072587a doi: 10.1021/jp072587a
19. [19]
  Cheong, D.; Panagiotopoulos, A. Z. Langmuir 2006, 22, 4076. doi: 10.1021/la053511d doi: 10.1021/la053511d
20. [20]
  Pool, R.; Bolhuis, P. G. J. Phys. Chem. B 2005, 109, 6650. doi: 10.1021/jp045576f doi: 10.1021/jp045576f
21. [21]
  Pool, R.; Bolhuis, P. G. Phys. Rev. Lett. 2006, 97, 018302. doi: 10.1103/PhysRevLett.97.018302 doi: 10.1103/PhysRevLett.97.018302
22. [22]
  Pool, R.; Bolhuis, P. G. Phys. Chem. Chem. Phys. 2006, 8, 941. doi: 10.1039/B512960E doi: 10.1039/B512960E
23. [23]
  Kawada, S.; Komori, M.; Fujimoto, K.; Yoshii, N.; Okazaki, S. Chem. Phys. Lett. 2016, 646, 36. doi: 10.1016/j.cplett.2015.12.062 doi: 10.1016/j.cplett.2015.12.062
24. [24]
  Fujimoto, K.; Kubo, Y.; Kawada, S.; Yoshii, N.; Okazaki, S. Mol. Simul. 2017, 43, 13. doi: 10.1080/08927022.2017.1328557 doi: 10.1080/08927022.2017.1328557
25. [25]
  Lifshitz, I. M.; Slyozov, V. V. J. Phys. Chem. Solids 1961, 19, 35. doi: 10.1016/0022-3697(61)90054-3 doi: 10.1016/0022-3697(61)90054-3
26. [26]
  Szabo, A.; Schulten, K.; Schulten, Z. J. Chem. Phys. 1980, 72, 4350. doi: 10.1063/1.439715 doi: 10.1063/1.439715
27. [27]
  Moore, W. J. Physical Chemistry, 4th ed. ; Prentice Hall, Inc. : Upper Saddle River, NJ, USA, 1972.
28. [28]
  Everett, D. H. Colloids Surf. 1986, 21, 41. doi: 10.1016/0166-6622(86)80081-6 doi: 10.1016/0166-6622(86)80081-6
29. [29]
  Yoshii, N.; Okazaki, S. Chem. Phys. Lett. 2006, 425, 58. doi: 10.1016/j.cplett.2006.05.004 doi: 10.1016/j.cplett.2006.05.004
30. [30]
  Yoshii, N.; Okazaki, S. Chem. Phys. Lett. 2006, 426, 66. doi: 10.1016/j.cplett.2006.05.038 doi: 10.1016/j.cplett.2006.05.038
31. [31]
  Aniansson, E. A. G.; Wall, S. N. J. Phys. Chem. 1974, 78, 1024. doi: 10.1021/j100603a016 doi: 10.1021/j100603a016
32. [32]
  Kestin, J.; Sokolov, M.; Wakeham, W. A. J. Phys. Chem. Ref. Data 1978, 7, 941. doi: 10.1063/1.555581 doi: 10.1063/1.555581
33. [33]
  The value obtained in Eq. (1) of Ref. 28 was used.
34. [34]
  Russel, W. B.; Saville, D. A.; Schowalter, W. R. Colloidal Dispersions; Cambridge University Press: Cambridge, UK, 1989.
35. [35]
  Kawada, S.; Fujimoto, K.; Yoshii, N.; Okazaki, S. J. Chem. Phys. 2017, 147, 084903. doi: 10.1063/1.4998549 doi: 10.1063/1.4998549
1. [1]
  Haojie Duan , Hejingying Niu , Lina Gan , Xiaodi Duan , Shuo Shi , Li Li . Reinterpret the heterogeneous reaction of α-Fe₂O₃ and NO₂ with 2D-COS: The role of SDS, UV and SO₂. Chinese Chemical Letters, 2024, 35(6): 109038-. doi: 10.1016/j.cclet.2023.109038
2. [2]
  Hongyi Li , Huiyun Wen , He Zhang , Jin Li , Xiang Cao , Jiaqing Zhang , Yutao Zheng , Saipeng Huang , Weiming Xue , Xiaojun Cai . Polymeric micelle-hydrogel composites design for biomedical applications. Chinese Chemical Letters, 2025, 36(5): 110072-. doi: 10.1016/j.cclet.2024.110072
3. [3]
  Xin-Yu Liu , He-Ying Mao , Jun-Sheng Hu , Tong-Rui Dou , Ben-Chi Liu , Chang-Xiu Lin , Jing-Shu Piao , Ming-Guan Piao . A c(RGDyK)-modified ROS-responsive polymeric micelle for hepatic stellate cell targeting. Chinese Chemical Letters, 2026, 37(1): 111237-. doi: 10.1016/j.cclet.2025.111237
4. [4]
  Weixu Li , Yuexin Wang , Lin Li , Xinyi Huang , Mengdi Liu , Bo Gui , Xianjun Lang , Cheng Wang . Promoting energy transfer pathway in porphyrin-based sp2 carbon-conjugated covalent organic frameworks for selective photocatalytic oxidation of sulfide. Chinese Journal of Structural Chemistry, 2024, 43(7): 100299-100299. doi: 10.1016/j.cjsc.2024.100299
5. [5]
  Jinqi Yang , Xiaoxiang Hu , Yuanyuan Zhang , Lingyu Zhao , Chunlin Yue , Yuan Cao , Yangyang Zhang , Zhenwen Zhao . Direct observation of natural products bound to protein based on UHPLC-ESI-MS combined with molecular dynamics simulation. Chinese Chemical Letters, 2025, 36(5): 110128-. doi: 10.1016/j.cclet.2024.110128
6. [6]
  Kangren Kong , Zaiqiang Ma , Yu Yin , Zhaoming Liu , Ruikang Tang . Nuclear magnetic resonance-guided Monte Carlo/molecular dynamics structure inference for amorphous solids. Chinese Journal of Structural Chemistry, 2026, 45(3): 100773-100773. doi: 10.1016/j.cjsc.2025.100773
7. [7]
  Yubo Tan , Ziying Wang , Yibo An , Man Li , Dazhuang Xu , Renyuan Liu , Xinyu Tan , Yaohui He , Zhixiang Lu , Gang Liu . Molecular engineering organometallic sonosensitizer for enhanced sonodynamic therapy via promoting ER stress-mediated HIF-1α degradation and cGAS-STING pathway activation. Chinese Chemical Letters, 2026, 37(3): 111214-. doi: 10.1016/j.cclet.2025.111214
8. [8]
  Kunya Wang , Bingyu Liu , Daojiang Yan , Jian Bai , Haibo Yu , Youcai Hu . Full biosynthetic pathway of pyrrolobenzoxazines. Chinese Chemical Letters, 2025, 36(1): 109811-. doi: 10.1016/j.cclet.2024.109811
9. [9]
  Zhimin Song , Zhe Tang , Yu Zhang , Yanru Zhou , Xiaozheng Duan , Yan Du , Chong-Bo Ma . DNA-modulated Mo-Zn single-atom nanozymes: Insights from molecular dynamics simulations to smartphone-assisted biosensing. Chinese Chemical Letters, 2025, 36(10): 110680-. doi: 10.1016/j.cclet.2024.110680
10. [10]
  Shiyang Sun , Ning Yang , Yaqiu Mao , Ting Wei , Pengli Wei , Tingting Yang , Yixin Zhang , Jian Yan , Changkai Jia , Yi Li , Xu Cai , Zhiyuan Zhao , Xuesong Feng , Xiaomei Zhuang , Wenpeng Zhang , Junhai Xiao , Pengyun Li , Zhibing Zheng , Song Li . Rational design of VHL-recruiting KRAS^G12C proteolysis-targeting chimeras based on molecular dynamics simulation. Chinese Chemical Letters, 2026, 37(2): 110992-. doi: 10.1016/j.cclet.2025.110992
11. [11]
  Huanyu Liu , Gang Yu , Ruoyao Guo , Hao Qi , Jiayin Zheng , Tong Jin , Zifeng Zhao , Zuqiang Bian , Zhiwei Liu . Direct identification of energy transfer mechanism in Ce^Ⅲ-Mn^Ⅱ system by constructing molecular heteronuclear complexes. Chinese Chemical Letters, 2025, 36(2): 110296-. doi: 10.1016/j.cclet.2024.110296
12. [12]
  Lizhi Wang , Chuanxin Wei , Xinyu Du , Yingying Zheng , Shuang Li , Ning Sun , Zhiqiang Zhuo , Ningning Yu , Yingru Lin , Zhiyang Sun , Jinyi Lin , Man Xu , Yongzheng Chang , Tianshi Qin , Zhoulu Wang , Xuehua Ding , Wei Huang . Energy engineering and mechanical elasticity of molecular crystals via supramolecular salt strategy for flexible visible optical waveguide. Chinese Chemical Letters, 2026, 37(2): 111634-. doi: 10.1016/j.cclet.2025.111634
13. [13]
  Shuangliang Xie , Yuyue Chen , Qing He , Liang Chen , Jikun Yang , Shiqing Deng , Yimei Zhu , He Qi . Relaxor antiferroelectric-relaxor ferroelectric crossover in NaNbO₃-based lead-free ceramics for high-efficiency large-capacitive energy storage. Chinese Chemical Letters, 2024, 35(7): 108871-. doi: 10.1016/j.cclet.2023.108871
14. [14]
  Hongxia Li , Xiyang Wang , Du Qiao , Jiahao Li , Weiping Zhu , Honglin Li . Mechanism of nanoparticle aggregation in gas-liquid microfluidic mixing. Chinese Chemical Letters, 2024, 35(4): 108747-. doi: 10.1016/j.cclet.2023.108747
15. [15]
  Jindian Duan , Xiaojuan Ding , Pui Ying Choy , Binyan Xu , Luchao Li , Hong Qin , Zheng Fang , Fuk Yee Kwong , Kai Guo . Oxidative spirolactonisation for modular access of γ-spirolactones via a radical tandem annulation pathway. Chinese Chemical Letters, 2024, 35(10): 109565-. doi: 10.1016/j.cclet.2024.109565
16. [16]
  Dongping Song , Tao Tu . The role of oceanic carbon pumps in Earth’s climate system: Impact and feedback under climate change. Chinese Chemical Letters, 2025, 36(8): 111300-. doi: 10.1016/j.cclet.2025.111300
17. [17]
  Dan-Ying Xing , Xiao-Dan Zhao , Chuan-Shu He , Bo Lai . Kinetic study and DFT calculation on the tetracycline abatement by peracetic acid. Chinese Chemical Letters, 2024, 35(9): 109436-. doi: 10.1016/j.cclet.2023.109436
18. [18]
  Xiumei LI , Yanju HUANG , Bo LIU , Yaru PAN . Syntheses, crystal structures, and quantum chemistry calculation of two Ni(Ⅱ) coordination polymers. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 2031-2039. doi: 10.11862/CJIC.20240109
19. [19]
  Xin Lu , Haoran Sun , Xiaomeng Li , Chunrui Li , Jinfeng Wang , Dandan Zhou . C14-HSL limits the mycelial morphology of pathogen Trichosporon cells but enhances their aggregation: Mechanisms and implications. Chinese Chemical Letters, 2024, 35(6): 108936-. doi: 10.1016/j.cclet.2023.108936
20. [20]
  Shuo Li , Qianfa Liu , Lijun Mao , Xin Zhang , Chunju Li , Da Ma . Benzothiadiazole-based water-soluble macrocycle: Synthesis, aggregation-induced emission and selective detection of spermine. Chinese Chemical Letters, 2024, 35(11): 109791-. doi: 10.1016/j.cclet.2024.109791

Get Citation

PDF

XML

Metrics

PDF Downloads(13)
Abstract views(957)
HTML views(145)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142