In this article we describe research on the synthesis and characterization of a family of "Janus" amphiphiles composed of disaccharide head groups and alkaloid units joined together via a methylene linker, and bearing a lateral aliphatic chain of varying length. The condensed phases formed by self-organization of the products as a function of temperature were characterized by differential scanning calorimetry, thermal polarized light microscopy, and small angle X-ray scattering, allied with computational modelling and simulations. Structural studies on heating specimens from the solid showed that some homologues exhibited lamellar, columnar and bicontinuous mesophases, whereas the same homologues revealed different phase sequences on cooling from the amorphous liquid. We explore these unusual results, which are revealed via supercooling.