Citation: Wang Yingxiong, Deng Manli, Tang Yongqiang, Han Yuchun, Huang Xu, Hou Yanbo, Wang Yilin. Aggregation of Biodegradable Cationic Gemini Surfactants with Amide or Ester Groups[J]. Acta Physico-Chimica Sinica, ;2020, 36(10): 190904. doi: 10.3866/PKU.WHXB201909046 shu

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: 2 December 2019
Available Online: 17 December 2019
Fund Project: 国家自然科学基金(21633002)资助项目国家自然科学基金 21633002

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.
- Cationic Gemini surfactant,
- Biodegradable,
- NMR,
- Micellization,
- Amide group,
- Ester group
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