The formation of temperature-, concentration-, and pH-responsive hydrogels composed of the symmetric long-chain bolaamphiphile dotriacontane-1,1'-diyl bis[[2-(dimethylammonio)ethyl]phosphate] (Me(2)PE-C32-Me(2)PE) was investigated by rheological, scattering, and spectroscopic techniques. At pH 5, this bolaamphiphile is known to form a dense network of helically structured nanofibers (Köhler et al. Soft Matter 2006, 2, 77-86). Rheological measurements and dynamic light scattering were used to describe the macroscopic behavior of the hydrogels. Small-angle neutron scattering (SANS) and time-resolved static light scattering were applied to get information about the morphology of the self-assembled aggregates. Finally, solid-state 31P NMR spectroscopy was used to gain insight into the mobility of the bolaamphiphile molecules within the fiber aggregates. In comparison with the previously examined trimethylammonio analogue PC-C32-PC, which forms temperature-dependent hydrogels, Me(2)PE-C32-Me(2)PE exhibits additional concentration- and pH-dependent gelling properties. The significantly higher stability of the Me(2)PE-C32-Me(2)PE hydrogel is supported by the SANS data, which indicate the presence of fiber aggregates up to 50 degrees C.

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The aggregation behavior of the bolaamphiphilic hydrogelators dotriacontane-1,32-diyl-bis[2-(trimethylammonio)ethylphosphate] (PC-C32-PC) and the pH-sensitive dotriacontane-1,32-diyl-bis[2-(dimethylammonio)-ethylphosphate] (Me2PE-C32-Me2PE) was characterized before using different methods. Dependent on the temperature, pH, and concentration, these bolaamphiphiles self-asssemble into long nanofibers or other aggregates, such as short rods or micelles. In order to obtain information about the motional dynamics and microscopic order inside of these aggregates, we carried out a systematic ESR spin probe study. The spectra obtained with the spin probes 5-, 12- and 16-doxyl stearic acid (n-DSA) were found to be highly sensitive to changes in the bolaamphiphilic arrangement. Rotational correlation times and order parameters were obtained from full ESR line shape simulations with the programs EasySpin and EPRSIM. The maximum hyperfine splitting, 2Amax, was used to determine the transition temperatures, which are in agreement with the DSCdata. By comparison of 5-DSA and 12-DSA, which are residing at different positions in the alkyl chain region of the aggregates, it was found that trans-gauche isomerization is predominantly occurring in the outer region of the aggregates. For Me2PE-C32-Me2PE at pH 10, our ESR data indicate that micelles are short rods rather than being spherical in shape. Therefore, increasing the concentration from 1 to 10 mg/mL leads only to a one-dimensional growth of these micelles.

The dynamical properties of water in hydrogels formed by the bolaamphiphiles dotriacontane-1,32-diyl-bis[2-(trimethylammonio)ethylphosphate] (PC-C32-PC) and its head group derivative dotriacontane-1,32-diyl-bis[2-(dimethylammonio)ethylphosphate] (Me(2)PE-C32-Me(2)PE) were investigated by determining the transverse relaxation times and the mean diffusion coefficients of the water protons. T(2) distributions obtained for hydrogels containing only 1 mg/mL of PC-C32-PC or Me(2)PE-C32-Me(2)PE were found to be almost unchanged compared to that of pure deionized water. In a hydrogel containing 30 mg/mL PC-C32-PC, a small dynamical perturbation of the water molecules could be observed, since the obtained major peak in the T(2) distribution was found to be slightly broadened and shifted to lower T(2) values with respect to pure water. Moreover, a slightly decreased mean diffusion coefficient of the water molecules was determined for the hydrogel with 30 mg/mL PC-C32-PC. For 30 mg/mL Me(2)PE-C32-Me(2)PE at pH 5, the dynamical properties of water are significantly influenced by the presence of the bolaamphiphiles. Whereas the mean diffusion coefficient of water was again only slightly decreased, the relaxation behavior was found to be considerably changed. At room temperature, the major T(2) peak obtained for 30 mg/mL Me(2)PE-C32-Me(2)PE at pH 5 was significantly broadened and shifted to lower T(2) values compared to pure buffer. This broad monomodal peak becomes bimodal when the temperature is decreased to 5 °C. Increasing the temperature revealed that the structural changes of the bolaamphiphilic self-assemblies at 45 °C are reflected in the determined mean relaxation times (T(2m)). These results indicate the presence of a significant degree of structural heterogeneity in a hydrogel formed by 30 mg/mL Me(2)PE-C32-Me(2)PE at pH 5. By comparing the mean diffusion coefficients with the mean transverse relaxation times, the distance scale of these heterogeneities could be estimated to be in the range of 50 to 120-140 μm. They can most probably be ascribed to the existence of a considerable number of lamellar domains being formed besides the nanofibers in hydrogels with 30 mg/mL Me(2)PE-C32-Me(2)PE at pH 5. Upon storage, the phenomenon of syneresis was observed for this hydrogel, which corresponds to a growth of the lamellar domains to sizes between 140 and 190 μm.