Emergence of Optical Activity and Surface Morphology Changes in Racemic Amino Acid Films Under Circularly Polarized Lyman-α Light Irradiation.

Abstract

The homochirality of life remains one of the most enigmatic issues in the study of the origin of life. A proposed mechanism for symmetry breaking involves irradiation by circularly polarized light (CPL). To investigate the photoreaction of amino acids under CPL irradiation, a vacuum ultraviolet (VUV) CPL irradiation system was developed at the synchrotron light source UVSOR-III. Hydrogen Lyman-α CPL (121.6 nm) is considered a potential asymmetric source in space. Therefore, racemic alanine film samples were irradiated with Lyman-α CPL to explore the photoreaction of biomolecules. Circular dichroism (CD) spectra measurements revealed that irradiation with right- (left-) handed CPL induced a positive (negative) anisotropy factor g in the wavelength range of 180-240 nm. However, the spectra differed from those of enantiopure alanine, exhibiting broad wavelength ranges and no sign change. Liquid chromatography-mass spectrometry (LC-MS) measurements indicate formation of larger molecules, such as oligomeric alanine adducts or modified oligomers after the Lyman-α CPL irradiation. Additionally, CPL irradiation considerably changes the microstructure of the alanine film surface, leading to the formation of circular network aggregates on the scale of 100 nm. The morphology changes in the alanine film and/or the formation of the larger molecules could be possible causes of the modified anisotropy factor spectra compared to those of enantiopure alanine. These findings highlight the need for further research on the photoreaction of biomolecules in solid states under VUV CPL irradiation, particularly in the photoionization energy range, to validate the cosmic scenario of homochirality.