English

Aggregation of Biodegradable Cationic Gemini Surfactants with Amide or Ester Groups

• Wang Yingxiong ^1,2, ,
• Deng Manli ^1, ,
• Tang Yongqiang ^1,3, ,
• Han Yuchun ^1, ,
• Huang Xu ^1, ,
• Hou Yanbo ^1,4, ,
• Wang Yilin ^{1, ,}

• 1.

  Key Laboratory of Colloid, Interface and Chemical Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China

• 2.

  Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, P. R. China

• 3.

  School of Chemical Engineering, Xi'an University, Xi'an 710065, P. R. China

• 4.

  Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, P. R. China

Corresponding author: Wang Yilin, yilinwang@iccas.ac.cn

• Received Date: 25 September 2019
  Revised Date: 02 December 2019
  Available Online: 15 October 2020
• Fund Project:

  国家自然科学基金(21633002)资助项目

Abstract: In the last thirty years, Gemini surfactants with various structures have been designed, synthesized, and demonstrated to show superior physicochemical properties. However, the utilization of non-degradable surfactants, including these Gemini surfactants, poses a threat to the environment; hence, degradable Gemini surfactants are desirable. Herein, biodegradable cationic Gemini surfactants with amide or ester groups in the hydrophobic chains or the spacer were synthesized. A monomeric surfactant containing an amide group and a Gemini surfactant with amide groups both in the hydrophobic chains and the spacer were synthesized for comparison. The effects of amide group location on the aggregation behavior of Gemini surfactants were studied systematically. The differences between the Gemini surfactants with amide groups and Gemini surfactants with ester groups were evaluated by comparing their aggregation behavior and hydrogen bonding formation. The Gemini surfactants with amide groups (C₁₂A-C_n-AC₁₂) in the chains showed much larger exothermic ΔH_mic and more negative ΔG_mic values than those of the corresponding monomeric surfactant C₁₂A; besides, their critical micelle concentration (cmc) was more than one order of magnitude lower than that of C₁₂A. The amide groups located in the hydrophobic alkyl chains promoted hydrogen bonding formation and self-assembly of the Gemini surfactants C₁₂A-C_n-AC₁₂. Moreover, ¹H NMR spectra revealed that the co-effect of a short spacer and hydrogen bonding leads to slow exchange of the C₁₂A-C₂-AC₁₂ molecules between the monomer and the aggregate. For the Gemini surfactant series C₁₂-AC_nA-C₁₂, the amide groups notably increased the spacer length, and largest cmc value and smallest exothermic ΔH_mic value were observed for C₁₂-AC₂A-C₁₂ instead of C₁₂-AC₆A-C₁₂. In C₁₂-AC₁₂A-C₁₂, the spacer was long and sufficiently flexible to adopt a "U"-shaped conformation above the cmc, and it acted as the hydrophobic part of the surfactant, as confirmed by ¹H NMR spectra. Among the Gemini surfactant with amide groups in both the spacer and the hydrophobic alkyl chains, C₁₂A-AC₆A-AC₁₂ had a smaller cmc and I₁/I₃ ratio as well as more exothermic ΔH_mic values than those of C₁₂A-C₆-AC₁₂ and C₁₂-AC₆A-C₁₂. ¹H NMR spectra indicated that an ester-alcohol structural equilibrium exists during aggregation for the Gemini surfactants with ester groups. In addition, the Gemini surfactants with ester groups formed water-mediated hydrogen bonds in the aggregates. This water-mediated hydrogen bonding between ester groups was weaker than the direct hydrogen bonding between amide groups. Therefore, the Gemini surfactants with ester groups, C₁₂E-C₆-EC₁₂ and C₁₂-EC₆E-C₁₂, exhibited lower surface activity, a larger micelle ionization degree, higher micropolarity, and smaller exothermic ΔH_mic and less negative ΔG_mic values than their counterparts with amide groups, C₁₂A-C₆-AC₁₂ and C₁₂-AC₆A-C₁₂.

Key words:
• Cationic Gemini surfactant
•  /  Biodegradable
•  /  NMR
•  /  Micellization
•  /  Amide group
•  /  Ester group

• 1. [1]

     Menger, F. M.; Littau, C. A. J. Am. Chem. Soc. 1991, 113, 1451. doi: 10.1021/ja00004a077

  2. [2]

     Menger, F. M.; Keiper, J. S. Angew. Chem. Int. Ed. 2000, 39, 1906. doi: 10.1002/1521-3773(20000602)39:11 < 1906::AIDANIE1906 > 3.0.CO; 2-Q

  3. [3]

     Huang, X.; Cao, M.W; Wang, J.B.; Wang, Y. L. J. Phys. Chem. B. 2006, 110, 19479. doi: 10.1021/jp0630121

  4. [4]

     Wang, Y. X.; Han, Y. C.; Huang, X.; Cao, M. W.; Wang, Y. L. J. Colloid Interface Sci. 2008, 319, 534. doi: 10.1016/j.jcis.2007.11.021

  5. [5]

     范雅珣, 韩玉淳, 王毅琳.物理化学学报, 2016, 32, 214. doi: 10.3866/PKU.WHXB201511022Fan, Y. X.; Han, Y. C.; Wang, Y. L. Acta Phys. -Chim. Sin. 2016, 32, 214. doi: 10.3866/PKU.WHXB201511022

  6. [6]

     Johnsson, M.; Wagenaar, A.; Engberts, J. B. F. N. J. Am. Chem. Soc. 2003, 125, 757. doi: 10.1021/ja028195t

  7. [7]

     Wagenaar, A.; Engberts, J. B. F. N. Tetrahedron 2007, 63, 10622. doi: 10.1016/j.tet.2007.08.023

  8. [8]

     Zana, R. J. Colloid Interface Sci. 1980, 78, 330. doi: 10.1016/0021-9797(80)90571-8

  9. [9]

     Pérez, L.; Pinazo, A.; Pons, R.; Infante, M. Adv. Colloid Interface Sci. 2014, 205, 134. doi: 10.1016/j.cis.2013.10.020

  10. [10]

      Tripathy, D. B.; Mishra, A.; Clark, J.; Farmer, T. Comptes Rendus Chim. 2018, 21, 112. doi: 10.1016/j.crci.2017.11.005

  11. [11]

      Tehrani-Bagha, A. R.; Holmberg, K.; van Ginkel, C. G.; Kean, M. J. Colloid Interface Sci. 2015, 449, 72. doi: 10.1016/j.jcis.2014.09.072

  12. [12]

      Qi, R. L.; Zhang, P. B.; Liu, J.; Zhou, L. Y.; Zhou, C. C.; Zhang, N.; Han, Y. C.; Wang, S.; Wang, Y. L. ACS Appl. Bio. Mater. 2018, 1, 21. doi: 10.1021/acsabm.8b00005

  13. [13]

      Tehrani-Bagha, A.; Holmberg, K. Curr. Opin Colloid Interface Sci. 2007, 12, 81. doi: 10.1016/j.cocis.2007.05.006

  14. [14]

      Hoque, J.; Gonuguntla, S.; Yarlagadda, V.; Aswal, V. K.; Haldar, J. Phys. Chem. Chem. Phys. 2014, 16, 11279. doi: 10.1039/c3cp55244f

  15. [15]

      Liang, Y. Q; Li, H.; Li, M.; Mao, X. M; Li, Y.; Wang, Z. H; Xue, L. Y.; Chen, X. H.; Hao, X. J. J. Mol. Liquids 2019, 280, 319. doi: 10.1016/j.molliq.2019.02.018

  16. [16]

      Fan, Y. R.; Li, Y. J.; Yuan, G. C; Wang, Y. L; Wang, J. B; Han, C. C.; Yan, H. K; Li, Z.; Thomas, R. K. Langmuir 2005, 21, 3814. doi: 10.1021/la047129x

  17. [17]

      Kalyanasundaram, K.; Thomas, J. K. J. Am. Chem. Soc. 1977, 99, 2039. doi: 10.1021/ja00449a004

  18. [18]

      Gottlieb, H. E.; Kotlyar, V.; Nudelman, A. J. Org. Chem. 1997, 62, 7512. doi: 10.1021/jo971176v

  19. [19]

      罗思琪, 王美娜, 赵微微, 王毅琳.物理化学学报, 2019, 35, 766. doi: 10.3866/PKU.WHXB201809038Luo, S. Q.; Wang, M. N.; Zhao, W. W.; Wang, Y. L. Acta Phys. -Chim. Sin. 2019, 35, 766. doi: 10.3866/PKU.WHXB201809038

  20. [20]

      Wang, X. Y.; Li, Y. J; Wang, J. B; Wang, Y. L; Ye, J. P.; Yan, H. K. J. Phys. Chem. B 2005, 109, 12850. doi: 10.1021/jp050651n

  21. [21]

      Kresheck, G. C.; Hargraves, W. A. J. Colloid Interface Sci. 1974, 48, 481. doi: 10.1016/0021-9797(74)90193-3

  22. [22]

      Sadaghiania, A. S.; Khan, A. J. Colloid Interface Sci. 1991, 144, 191. doi: 10.1016/0021-9797(91)90250-C

  23. [23]

      Zana, R. Langmuir 1996, 12, 1208. doi: 10.1021/la950691q

  24. [24]

      陈晓瑛, 俞刚金, 毛诗珍, 刘买利, 杜有如.波谱学杂志, 2019, 36, 219. doi: 10.11938/cjmr20172610Chen, X. Y.; Yu, G. J.; Mao, S. Z.; Liu, M. L.; Du, Y. R. Chinese J. Mag Res. 2019, 36, 219. doi: 10.11938/cjmr20172610

  25. [25]

      Zana, R.; Benrraou, M.; Rueff, R. Langmuir 1991, 7, 1072. doi: 10.1021/la00054a008

  26. [26]

      Tanford, C. J. Phys. Chem. 1972, 76, 3020. doi: 10.1021/j100665a018

  27. [27]

      陈晓瑛, 俞刚金, 毛诗珍, 刘买利, 杜有如.波谱学杂志, 2018, 35, 75. doi: 10.11938/cjmr20172577Chen, X. Y.; Yu, G. J.; Mao, S. Z.; Liu, M. L.; Du, Y. R. Chin. J. Mag Res. 2018, 35, 75. doi: 10.11938/cjmr20172577

  28. [28]

      Shimizu, S.; El Seoud, O. A. Langmuir 2003, 19, 238. doi: 10.1021/la026286y

  29. [29]

      Wettig, S. D.; Verrall, R. E. J. Colloid Interface Sci. 2001, 235, 310. doi: 10.1006/jcis.2000.7348

  30. [30]

      Wettig, S. D.; Verrall, R. E. J. Colloid Interface Sci. 2001, 235, 310. doi: 10.1006/jcis.2000.7348

  31. [31]

      Zana, R. J. Colloid Interface Sci. 2002, 248, 203. doi: 10.1006/jcis.2001.8104

  32. [32]

      Fung, B. M.; Mamrosh, D. L.; O'Rear, E. A.; Frech, C. B.; Afzal, J. J. Phys. Chem. 1988, 92, 4405. doi: 10.1021/j100326a032

  33. [33]

      Guo, W.; Brown, T. A.; Fung, B. M. J. Phys. Chem. 1991, 95, 1829. doi: 10.1021/j100157a060

  34. [34]

      Kondo, Y.; Miyazawa, H.; Sakai, H.; Abe, M.; Yoshino, N. J. Am. Chem. Soc. 2002, 124, 6516. doi: 10.1021/ja0178564

  35. [35]

      Leyendekkers, J. V. J. Chem. Soc. Faraday Trans. 1982, 78, 357. doi: 10.1039/F19827800357

  36. [36]

      Huc, I.; Oda, R. Chem. Commun. 1999, 20, 2025. doi: 10.1039/A906141J

  37. [37]

      Danino, D.; Talmon, Y.; Zana, R. Langmuir 1995, 11, 1448. doi: 10.1021/la00005a008

  38. [38]

      Zana, R.; Talmon, Y. Nature 1993, 362, 228. doi: 10.1038/362228a0

  39. [39]

      Gillitt, N. D.; Savelli, G.; Bunton, C. A. Langmuir 2006, 22, 5570. doi: 10.1021/la0606695

  40. [40]

      Ulmius, J.; Wennerström, H. J. Mag. Res. 1977, 28, 309. doi: 10.1016/0022-2364(77)90161-5

  41. [41]

      Das, S.; Bhirud, R. G.; Nayyar, N.; Narayan, K. S.; Kumar, V. V. J. Phys. Chem. 1992, 96, 7454. doi: 10.1021/j100197a059

  42. [42]

      Villeneuve, M.; Ootsu, R.; Ishiwata, M.; Nakahara, H. J. Phys. Chem. B 2006, 110, 17830. doi: 10.1021/jp062145j

•