title: Correlations of properties and structures at different length scales of hydro- and organo-gels based on N-alkyl-(R)-12-hydroxyoctadecylammonium chlorides.
abstract: The self-assembly and gelating ability of a set of N-alkyl-(R)-12-hydroxyoctadecylammonium chlorides (NCl-n, where n = 0-6, 18 is the length of the alkyl chain on nitrogen) are described. Several are found to be ambidextrous (gelating both water and a variety of organic liquids) and very efficient (needing less than ca. 0.5 wt % at room temperature). Structure-property correlations at different distance scales of the NCl-n in their hydro- and organo-gels and neat, solid states have been made using X-ray diffraction, neutron scattering, thermal, optical, cryo-SEM and rheological techniques. The self-assembled fibrillar networks consist of spherulitic objects with fibers whose diameters and degrees of twisting differ in the hydro- and organo-gels. Increasing n (and, thus, the molecular length) increases the width of the fibers in their hydrogels; an irregular, less pronounced trend between n and fiber width is observed in the corresponding toluene gels. Time-dependent, small angle neutron scattering data for the isothermal sol-to-gel transformation of sols of NCl-18/toluene to their gels, treated according to Avrami theory, indicate heterogeneous nucleation involving rodlike growth. Rheological studies of gels of NCl-3 in water and toluene confirm their viscoelastic nature and show that the hydrogel is mechanically stronger than the toluene gel. Models for the different molecular packing arrangements within the fibrillar gel networks of the hydro- and organogels have been inferred from X-ray diffraction. The variations in the fibrillar networks provide a comprehensive picture and detailed insights into why seemingly very similar NCl-n behave very differently during their self-assembly processes in water and organic liquids. It is shown that the NCl-n provide a versatile platform for interrogating fundamental questions regarding the links between molecular structure and one-dimensional self-aggregation, leading to gelation.
authors: Department of Chemistry, Georgetown University, Washington, DC 20057-1227, United States.
authors: V Ajay
authors: VA
authors: Mallia
authors: Pierre
authors: P
authors: Terech
authors: Richard G
authors: RG
authors: Weiss