Unprecedented Relationship Between the Size of Spherical Chiral Micellar Aggregates and Their Specific Optical Rotations

Abstract

Transmission electron microscopy (TEM) images and fluorescence quenching methods indicated that lauryl ester of L-phenylalanine (LEP) and lauryl ester of L-tyrosine (LET) form spherical chiral micelles in the 50-200 mM range and their size increases with concentration. The number of molecules present in these spherical chiral aggregates varied from 80 to 160 for LEP and 80-100 for LET. The specific optical rotation, representing circular birefringence, for LEP at 405 nm and 32 °C is found to increase linearly from 37 deg cc g(-1) dm(-1) for an isolated molecule to 56 deg cc g(-1) dm(-1) for ∼200 nm size aggregate. A similar trend was found for temperatures up to 70 °C and at other visible wavelengths. A linear relation between specific optical rotation and the size of aggregate is also observed for LET. Circular dichroism, as measured in both the visible and infrared wavelength regions, however did not reveal any concentration dependent changes. The unique sensitivity uncovered for specific optical rotation as a function of the size of spherical chiral aggregates is unprecedented and opens new areas of enquiry for physical chemists.