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Coacervation of Cationic Gemini Surfactant with N-Benzoylglutamic Acid in Aqueous Solution
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文摘
Coacervation of cationic gemini surfactant hexamethylene-1,6-bis(dodecyldimethylammonium bromide) (12鈥?鈥?2) with pH-sensitive N-benzoylglutamic acid (H2Bzglu) has been investigated by potentiometric pH-titration, turbidity titration, dynamic light scattering (DLS), isothermal titration calorimetry (ITC), TEM, 1H NMR, and light microscopy. Phase boundaries of the 12鈥?鈥?2/H2Bzglu mixture were obtained over the pH range from 2 to 9 and in the H2Bzglu concentration range from 30.0 to 50.0 mM at pH 4.5. When the H2Bzglu concentration is beyond 30.0 mM, the 12鈥?鈥?2/H2Bzglu mixed solution undergoes the phase transitions from soluble aggregate, to precipitate, coacervate, and soluble aggregate again as pH increases. The results indicate that coacervation occurs at extremely low 12鈥?鈥?2 concentration and lasts over a wide surfactant range, and can be enhanced or suppressed by changing pH, 12鈥?鈥?2/H2Bzglu molar ratio and H2Bzglu concentration. The coacervates present a disorderly connected lay structure. Coacervation only takes place at pH 4鈥?, where the aggregates are nearly charge neutralized, and a minimum H2Bzglu concentration of 30.0 mM is required for coacervation. In this pH range, H2Bzglu mainly exist as HBzglu鈥?/sup>. The investigations on intermolecular interactions indicate that the aggregation of 12鈥?鈥?2 is greatly promoted by the strong electrostatic and hydrophobic interactions with the HBzglu鈥?/sup> molecules, and the interaction also promotes the formation of dimers, trimers, and tetramers of HBzglu鈥?/sup> through hydrogen bonds. The double chains of 12鈥?鈥?2 and the HBzglu鈥?/sup> oligomers can play the bridging roles connecting aggregates. These factors endow the mixed system with a very high efficiency in generating coacervation.

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