A promising system of mixed single- and double-short-tailed PEO ether phosphate esters: phase behavior and vesicle formation.

A promising system of mixed single- and double-short-tailed PEO ether phosphate esters: phase behavior and vesicle formation.
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DOI:
10.1016/j.jcis.2006.06.059
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发表时间:
2006-10
影响因子:
9.9
通讯作者:
Zaiwu Yuan;J. Hao;H. Hoffmann
Zaiwu Yuan;J. Hao;H. Hoffmann
中科院分区:
化学1区
文献类型:
--
作者:
Zaiwu Yuan;J. Hao;H. Hoffmann

文献摘要

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Acidic surfactants, single- and bi-2-methylheptanol polyethenoxy ether phosphate esters, H2PO3(OCH2CH2)nOCH2CH2CH2CH2CH2CH(CH3)2(u-MHPEPE) and HPO3[(OCH2CH2)nOCH2CH2CH2CH2CH2CH(CH3)2]2(d-MHPEPE), where n≈4, were synthesized. Phase behavior of u- and d-MHPEPE (u- and d-MHPEPE mixtures were abbreviated as MHPEPE) mixtures in aqueous solutions and vesicle formation were determined. Surface tension measurements showed that u-MHPEPE and MHPEPE have low surface tensions at critical micelle concentrations. γcmc=29.0 mNm−1and cmc=16.0 mmolL−1for u-MHPEPE, MHPEPE has two transition points suggesting the mixtures of u- and d-MHPEPE with γcmc1=30.5 mNm−1and cmc1=4.0 mmolL−1, and γcmc2=27.3 mNm−1and cmc2=42.0 mmolL−1. These values, specific γcmc, are much lower than those of traditionally cationic or anionic surfactants such as cetyltrimethylammonium bromide (CTAB, γcmc=37.1 mNm−1at cmc=0.92 mmolL−1) and sodium dodecyl sulfate (SDS, γcmc=39.0 mNm−1at cmc=8.1 mmolL−1). Rich phase behavior was observed with increasing MHPEPE concentration, an isotropic L1-phase (micelle solution), an unstable emulsion-region (with time, the samples separate into two-phase), a transparently bluish and birefringent Lα-phase up to 200 mmol L−1with unilamellar and multilamellar vesicles. These unilamellar and multilamellar vesicles were demonstrated by using staining transmission electron microscopy (staining-TEM), which were compared to freeze-fracture TEM (FF-TEM). The vesicle-phase is stable for at least 1 year. Vesicle formation possibly could be explained in harmonization of the hydrophobic force of acidic surfactant tails, the hydrogen bonding (H-bonding) and the electrostatic interaction among polar headgroups of PEO ether phosphate ester. Phase transition from the flow birefringent unilamellar vesicles induced by addition of HCl, NaCl, NaOH, and increasing temperature has been observed. Surprisingly, for u-MHPEPE or d-MHPEPE in water, we just observed L1-phase (micelle solution) with increasing u-MHPEPE or d-MHPEPE concentration.