Mechanism of pH-dependent photolysis of aliphatic amino acids and enantiomeric enrichment of racemic leucine by circularly polarized light.
It has been proposed that the origin of biological homochirality may be the result of irradiation of a racemic sample of amino acids by circularly polarized light (CPL). To determine the mechanism of enantiomeric enrichment, the irradiation of aliphatic amino acids by CPL was undertaken. An enantiomerically enriched sample (e.g., L isomer enrichment from r-CPL) was found to result from the preferential excitation/decomposition of one enantiomer over another via a Norrish Type II mechanism (leucine, valine, and isoleucine), with the enantiomeric excess dependent on the degree of protonation of the amino/carboxylic acid moiety.
Nishino
H
H
Inoue Photochirogenesis Project, ERATO, JST, 4-6-3 Kamishinden, Toyonaka 560-0085, Japan.
Kosaka
A
A
Hembury
G A
GA
Shitomi
H
H
Onuki
H
H
Inoue
Y
Y
D000596:Amino Acids / Q000737:chemistry* / Q000528:radiation effects; D002942:Circular Dichroism; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D007930:Leucine / Q000737:chemistry* / Q000528:radiation effects; D008968:Molecular Conformation; D010782:Photolysis; D013237:Stereoisomerism
D000596:Amino Acids; D007930:Leucine