Raman and IR spectroscopic studies of the interaction between counterion and polar group in self-assembled systems of AOT-homologous “sodium dialkyl sulfosuccinates’'
作者:Yasuyuki Nagasoe、Naoki Ichiyanagi、Hirofumi Okabayashi、Sandrine Nave、Julian Eastoe、Charmian J. O'Connor
DOI:10.1039/a904815d
日期:——
Headgroupâcounterion interactions have been studied for a homologous series of sodium dialkyl sulfosuccinates (SDAS) with propyl, butyl, hexyl, octyl, decyl, undecyl and dodecyl chains as Aerosol-OT analogues. Raman scattering and IR absorption spectra were recorded and compared with those for dimethyl sulfosuccinate monohydrate, diethyl sulfosuccinate trihydrate and diheptyl sulfosuccinate dihydrate, whose crystal structures are known. The spectral features of the C2O and SO3- stretch modes directly reflect the interaction between the polar group and the Na+ ion and depend strongly upon the environment of hydration. The results may be summarized as follows. For the SDAS monohydrates in the solid state, there exists a strong interaction between the β C2O group and the Na+ ion, as a consequence of coordination of the β C2O to the Na+ ion, resulting in splitting of the C2O stretch modes. In particular, the common Raman (IR) bands observed at 1705â1707 (1706â1708) and 1730â1732 (1732â1733) cm-1 may be assigned to the β C2O group coordinated to the Na+ counterion and the hydrated α C2O group, respectively. The extent of splitting of these bands is a measure of the strength of this C2O···Na+ interaction. Coordination of the β C2O to the Na+ ion also affects the C2O deformation modes of the OâC2O linkage. An increased hydration number and longer hydrocarbon chains induce a weak interaction between the C2O group and the Na+ ion. The SO3-···Na+ interaction reflects the SO3- stretch modes, depending upon the extent of hydration. Furthermore, for the SDAS samples in the organic and aqueous microphases, Raman (IR) bands characteristic of the C2O and SO3-1 groups have been used successfully to account for the interaction between the polar group and the Na+ ion.
头基–对离子相互作用已被研究一系列同系物的硫酸二烷基琥珀酸钠(SDAS),其烷基链包括丙基、丁基、己基、辛基、癸基、十一烷基和十二烷基,作为气溶胶-OT的类似物。记录并比较了拉曼散射和红外吸收光谱,并与已知晶体结构的单水合二甲基琥珀酸、三水合二乙基琥珀酸和二水合二庚基琥珀酸的光谱特征进行了比较。C=O和SO₃⁻的伸缩模式的光谱特征直接反映了极性基团与Na⁺离子之间的相互作用,并且强烈依赖于水合环境。结果可总结如下:在固态的SDAS单水合物中,β C=O基团与Na⁺离子之间存在强相互作用,这是由于β C=O与Na⁺离子的配位,导致C=O伸缩模式的分裂。特别是,在1705–1707 cm⁻¹(1706–1708 cm⁻¹)和1730–1732 cm⁻¹(1732–1733 cm⁻¹)观察到的常见拉曼(红外)特征带可以分别归因于与Na⁺对离子配位的β C=O基团和水合的α C=O基团。这些特征带的分裂程度是C=O· · ·Na⁺相互作用强度的衡量。β C=O与Na⁺离子的配位还影响O–C=O连接的C=O变形模式。增加的水合数和较长的烃链会导致C=O基团与Na⁺离子之间的弱相互作用。SO₃⁻· · ·Na⁺的相互作用反映了SO₃⁻的伸缩模式,依赖于水合程度。此外,对于有机和水相微相中的SDAS样品,C=O和SO₃⁻基团特征的拉曼(红外)特征带已成功用于解释极性基团与Na⁺离子之间的相互作用。