title: A systematic investigation and insight into the formation mechanism of bilayers of fatty acid/soap mixtures in aqueous solutions.
abstract: Vesicles are the most common form of bilayer structures in fatty acid/soap mixtures in aqueous solutions; however, a peculiar bilayer structure called a "planar sheet" was found for the first time in the mixtures. In the past few decades, considerable research has focused on the formation theory of bilayers in fatty acid/soap mixtures. The hydrogen bond theory has been widely accepted by scientists to explain the formation of bilayers. However, except for the hydrogen bond, no other driving forces were proposed systematically. In this work, three kinds of weak interactions were investigated in detail, which could perfectly demonstrate the formation mechanism of bilayer structures in the fatty acid/soap mixtures in aqueous solutions. (i) The influence of hydrophobic interaction was detected by changing the chain length of fatty acid (C(n)H(2n+1)COOH), in which n = 10 to 18, the phase behavior was investigated, and the phase region was presented. With the help of cryogenic transmission electron microscopy (cryo-TEM) observations, deuterium nuclear magnetic resonance ((2)H NMR), and X-ray diffraction (XRD) measurements, the vesicles and planar sheets were determined. The chain length of C(n)H(2n+1)COOH has an important effect on the physical state of the hydrophobic chain, resulting in an obvious difference in the viscoelasticity of the solution samples. (ii) The existence of hydrogen bonds between fatty acids and their soaps in aqueous solutions was demonstrated by Fourier transform infrared (FT-IR) spectroscopy and molecule dynamical simulation. From the pH measurements, the pH ranges of the bilayer formation were at the pKa values of fatty acids, respectively. (iii) Counterions can be embedded in the stern layer of the bilayers and screen the electrostatic repulsion between the COO(-) anionic headgroups. FT-IR characterization demonstrated a bidentate bridging coordination mode between counterions and carboxylates. The conductivity measurements provided the degree of counterion binding (β = 0.854), indicating the importance of the counterions.
authors.affiliation: Key Laboratory of Colloid and Interface Chemistry and Key Laboratory of Special Aggregated Materials, Shandong University, Ministry of Education , Jinan 250100, P. R. China.
authors.forename: Wenlong
authors.initials: W
authors.lastname: Xu
authors.forename: Aixin
authors.initials: A
authors.lastname: Song
authors.forename: Shuli
authors.initials: S
authors.lastname: Dong
authors.forename: Jingfei
authors.initials: J
authors.lastname: Chen
authors.forename: Jingcheng
authors.initials: J
authors.lastname: Hao
mesh_terms: D004563:Electrochemistry; D005227:Fatty Acids / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008823:Micelles; D012915:Soaps / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
chemical_list: D005227:Fatty Acids; D008823:Micelles; D012915:Soaps; D014867:Water