Understanding photochirogenesis: solvent effects on circular dichroism and anisotropy spectroscopy.
The basic units that constitute essential biopolymers (proteins and nucleic acids) are enantiomerically biased. Proteins are constructed from L-amino acids and nucleic acids possess a backbone composed exclusively of D-sugars. Photochirogenesis has been postulated to be the source of this homochirality of biomolecules: Asymmetric photochemical reactions were catalyzed by circularly polarized light (cpl) in interstellar environments and generated the first chiral prebiotic precursors. Enantiomers absorb cpl differently and this difference can dictate the kinetics of asymmetric photochemical reactions. These differences in absorption can be studied using circular dichroism (CD) and anisotropy spectroscopy. Rather than measuring the CD spectrum alone, the anisotropy factor g is recorded (CD divided by absorption). This factor g is directly related to the maximum achievable enantiomeric excess. We now report on the substantial influence of solvent and molecular surroundings on CD and anisotropy spectroscopy. This shows for the first time that CD and anisotropy signals depend just as much on the molecular surroundings of a molecule as on the nature of the molecule itself. CD and g spectra of amino acids in different solvents and in the solid state are presented here and the influence of these different surroundings on the spectra is discussed.
Institute for Applied and Physical Chemistry, University of Bremen, Bremen, Germany.
Jan Hendrik
JH
Bredehöft
Nykola C
NC
Jones
Cornelia
C
Meinert
Amanda C
AC
Evans
Søren V
SV
Hoffmann
Uwe J
UJ
Meierhenrich
D000596:Amino Acids / Q000737:chemistry*; D016880:Anisotropy; D002942:Circular Dichroism; D008958:Models, Molecular; D008968:Molecular Conformation; D055668:Photochemical Processes; D012997:Solvents / Q000737:chemistry*; D013237:Stereoisomerism
D000596:Amino Acids; D012997:Solvents
amino acids; asymmetric photochemistry; interstellar medium; origins of life; synchrotron radiation