Fmoc-Ala-Ala
and Fmoc-Ala-Lac are spectrally distinct in both their
gelled and nongelled forms. Carbonyl bonds are highlighted in the
chemical structures of Fmoc-Ala-Ala (A, top) and Fmoc-Ala-Lac (A,
bottom), and the resonance stretching frequencies of these particular
bonds are highlighted in the same color in the IR spectra of solutions
in ethanol (B, top) and gels in water (B, bottom). The spectral overlap
can be correlated with carbonyl features, with the carbamate linker’s
carbonyl stretching (purple) and the terminal carboxylic acid carbonyl
(gray) common to Fmoc-Ala-Ala, Fmoc-Ala-Lac, and Fmoc-Ala (structure
not shown). CD spectra (C) show a marked increase in dichroism in
the gelled state (solid lines) relative to that in the solution state
(high pH, dashed lines) in both Fmoc-Ala-Ala and Fmoc-Ala-Lac, indicating
induced chirality as a result of self-assembly. Large peaks above
280 nm indicate the interaction of aromatic Fmoc groups within a chiral
assembly.