Synthesis and Properties of pH and Redox Dual-switchable Surfactant†

doi:10.7503/cjcu20170054

Abstract

Abstract:

A new dual-stimuli responsive surfactant intermediate 11-tertiary aminehendecyl-carbonyl-ferrocenyl(C₁₁-N-Fe) was synthesized. The structure of the product was characterized by mass spectra and ¹H NMR. The dual-stimuli responsive properties of C₁₁-N-Fe were investigated by optical transmittance and cyclic voltammograms. The results show that C₁₁-N-Fe has good dual-stimuli properties. pH and redox dual-stimulated responsive foams can be prepared by C₁₁-N-Fe hydrochloride surfactant. Moreover, the defoaming process triggered pH or redox reaction can be completed within 2 min. C₁₁-N-Fe hydrochloride surfactant can also act as the emulsifier for n-decane/water system, because of it contains rigid ferrocenyl on hydrophobic chain. The C₁₁-N-Fe hydrochloride emulsion with uniform particle size can be prepared. Besides, the stability of the emulsion becomes more stable with increasing of the concentration of C₁₁-N-Fe hydrochloride surfactant. Furthermore, the emulsion can also be triggered by pH and redox dual-stimuli.

Key words: Surfactant, pH-stimuli, Redox-stimuli, Foam, Emulsion

CLC Number:

O647

TrendMD:

YIN Jinchao, CHEN Yukai, JIANG Jianzhong, CUI Zhenggang. Synthesis and Properties of pH and Redox Dual-switchable Surfactant^†[J]. Chem. J. Chinese Universities, 2017, 38(9): 1645.

Figures/Tables 10

Scheme 1 Molecular structures of C11-N-Fe and illustration of pH-redox stimuli responses at the air/liquid or oil/water interface

Scheme 2 Synthetic route of C11-N-Fe

Fig.1 Optical transmittance changes of C11-N-Fe aqueous solution(1×10-3 mol/L)after adding NaOH(solid time) and HCl(dashed line)

Table 1 Surface activity parameter of C11-N-Fe surfactant before and after oxidation in the air/water interface(25 ℃)

Surfactant	cmc/(mol·L^-1)	γ_cmc/(mN·m^-1)	A/nm²
C₁₁-N-Fe	1.25×10^-3	47.93	0.6139
C₁₁-N-Fe-O_x	2.5×10^-3	54.62	0.7488

Fig.2 C11-N-Fe hydrochloride γ-lgc graph(25 ℃) before(a) and after oxidation(b)(A), cyclic voltammograms(100 mV/s)(B), UV-Vis spectra of C11-N-Fe ethanol solution(1×10-3 mol/L) before and after oxidation and reduction(C) and the change in absorbance at 455 nm while C11-N-Fe(1×10-3 mol/L) before and after oxidized by H2O2 and reduced by electrification

Fig.3 Foam volume(A) and the foam volume change with time(B) for 7×10-3 mol/L

Fig.4 Foam volume of C11-N-Fe hydrochloride aqueous solution(7×10-3 mol/L)(A) alternate adding NaOH(B), HCl(C), oxidized by adding H2O2(D) and reduced by electrification(E)

Fig.5 Photographs(A, B) and selected optical micrographs(C) of n-decane-in-water emulsions(volume ratio, 1∶1) stabilized by C11-N-Fe hydrochloride surfactant alone(A) Taken one day; (B, C) one month after preparation. The concentration of C11-N-Fe hydrochloride in the aqueous phase from(Ⅰ) to (Ⅵ) is 1×10-3, 1.3×10-3, 1.6×10-3, 2×10-3, 3×10-3, 4×10-3 mol/L respectively; (C) Concentration of C11-N-Fe hydrochloride in the aqueous/(mol·L-1): (C1) 1×10-3; (C2) 1.6×10-3; (C3) 2×10-3; (C4) 4×10-3.

Fig.6 Photographs(A) and corresponding optical micrographs(B—D) of n-decane-in-water emulsions stabilised by 1.6×10-3 mol/L C11-N-Fe hydrochloride alternate adding NaOH/HCl undergoing switching off/on cycle(B) Stable emulsion; (C) after adding NaOH; (D) afte adding HCl followed by homogenization for 2 min.

Fig.7 Photographs(A) and corresponding optical micrographs(B—D) of n-decane-in-water emulsions stabilized by 1.6×10-3 mol/L C11-N-Fe hydrochloride oxidation by H2O2 and reduction by electrification undergoing switching off/on cycle(B) Stable emulsion; (C) after oxidation by H2O2; (D) after reduction by electrified followed by homogenization for 2 min.

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