Self-Assembly and Polymerization of Diacetylene-Containing Peptide Amphiphiles in Aqueous Solution

A systematic study was performed of the fiber forming properties and polymerization characteristics of two peptide amphiphiles containing a diacetylene functionality in the alkyl tail comprising 23 and 25 C atoms, respectively. Both diyne containing peptide amphiphiles were able to form stable beta-sheet fibers of micrometers length in an aqueous solution. However, there was a large difference between the stability of the two amphiphiles. This was shown by a large difference in assembly and disassembly temperature and by different behavior during polymerization. Because the monomers were preorganized with a tight molecular packing, the polymerization could be carried out using wavelengths up to 532 nm. For both amphiphiles, the fiber structure did not change when the polymerization was carried out at an elevated temperature. The degree of polymerization, however, barely decreased for the longer amphiphile (2) but showed a gradual decline for the shorter one (1) when the temperature was raised from room temperature to the melting temperature of the fibers. Furthermore, the pH did not influence the fiber assembly for 2, but hampered it for I at alkaline pH. The fiber structure was, for both of the amphiphiles, not dependent on the pH. After polymerization, the molecular packing of the amphiphiles was only slightly influenced by an increase in temperature, as indicated by the small color change of polymerized fibers, which was also reversible. Additionally, pH had no influence on the assembly structure, as indicated by the color of the polymer which was the same at all pH values. Thus, both fibers increased in stability upon polymerization. The large difference in assembly and polymerization behavior of the two similar-looking amphiphiles 1 and 2, with a 23 or 25 carbon tail, is indicative of the subtlety of the assembly and disassembly processes in these fibrous architectures.