Effect of the Substituent Position on the Phase Behavior and Photoresponsive Dynamic Behavior of Mixed Systems of a Gemini Surfactant and trans-Methoxy Sodium Cinnamates.

ABSTRACT

Mixed systems of the Gemini cationic surfactant trimethylene-1,3-bis (dodecyldimethylammonium bromide) (12-3-12·2Br-) and the photosensitive additives trans-methoxy sodium cinnamates with different substituent positions (trans-ortho-methoxy cinnamate, trans-OMCA; trans-meta-methoxy cinnamate, trans-MMCA; and trans-para-methoxy cinnamate, trans-PMCA) were selected for investigating the effects of the substituting position of methoxy on the system phase diagram and UV light-responsive behavior of the wormlike micelles. The differences in phase behaviors of the selected systems were analyzed by calculating the potential distribution, molecular volume, and free energy of solvation of cinnamates and the binding energies between photosensitive additives and the surfactant. The photoresponsive behaviors of wormlike micelle solutions formed in the selected systems were studied by the rheological method and UV-vis and H nuclear magnetic resonance (1H NMR) spectroscopy; the kinetics of photoisomerization of trans-OMCA, trans-MMCA, and trans-PMCA were studied by first-order derivative spectrophotometry. The results reveal that the methoxy substituent position has a great influence on the phase behavior and photosensitivity of the studied systems. In addition, the photoisomerization of the studied cinnamates follows the first-order opposite reaction laws; the different reaction rates play the decisive role in the photosensitivity of the wormlike micelles. This paper would afford a deeper understanding of the UV light-responsive mechanism at the molecular level and provide essential guidance in preparing smart materials with adjustable light sensitivity.