Chiroptical activity of hydroxycarboxylic acids with implications for the origin of biological homochirality

Circularly polarised light (CPL) interacting with interstellar organic molecules might have imparted chiral bias and hence preluded prebiotic evolution of biomolecular homochirality. The l-enrichment of extra-terrestrial amino acids in meteorites, as opposed to no detectable excess in monocarboxylic acids and amines, has previously been attributed to their intrinsic interaction with stellar CPL revealed by substantial differences in their chiroptical signals. Recent analyses of meteoritic hydroxycarboxylic acids (HCAs) – potential co-building blocks of ancestral proto-peptides – indicated a chiral bias toward the l-enantiomer of lactic acid. Here we report on novel anisotropy spectra of several HCAs using a synchrotron radiation electronic circular dichroism spectrophotometer to support the re-evaluation of chiral biomarkers of extra-terrestrial origin in the context of absolute photochirogenesis. We found that irradiation by CPL which would yield l-excess in amino acids would also yield l-excess in aliphatic chain HCAs, including lactic acid and mandelic acid, in the examined conditions. Only tartaric acid would show “unnatural” d-enrichment, which makes it a suitable target compound for further assessing the relevance of the CPL scenario.

Chiroptical activity of hydroxycarboxylic acids: implications for the origin of biological homochirality

Circularly polarised light (CPL) interacting with interstellar organic molecules might have imparted chiral bias and hence preluded prebiotic evolution of biomolecular homochirality. The l-enrichment of extra-terrestrial amino acids in meteorites, as opposed to no detectable excess in monocarboxylic acids and amines, has previously been attributed to their intrinsic interaction with stellar CPL revealed by substantial differences in their chiroptical signals. Recent analyses of meteoritic hydroxycarboxylic acids (HCAs) – potential co-building blocks of ancestral proto-peptides – showed an enantiomeric excess in l-lactic acid. Here we report on novel anisotropy spectra of several HCAs using a synchrotron radiation electronic circular dichroism spectrophotometer to support the re-evaluation of chiral biomarkers of extra-terrestrial origin in the context of absolute photochirogenesis. We found that irradiation by CPL which would yield l-excess in amino acids would also yield lexcess in aliphatic chain HCAs including lactic acid as well as mandelic acid in the examined conditions. Only tartaric acid would show “unnatural” d-enrichment, which makes it a suitable target compound for further assessing the relevance of the CPL scenario.

Chiroptical characterization tools for asymmetric small molecules – experimental and computational approaches for electronic circular dichroism (ECD) and anisotropy spectroscopy

Experimental and computational electronic circular dichroism spectra are used in conjunction with anisotropy spectra to chiroptically characterize mandelic acid and its derivatives into the vacuum UV.

Probing of Higher Excited States of Merocyanine Derivatives of Azaazulene and Indandione by Fluorescence Excitation Anisotropy Spectra

This paper is dedicated to the spectral and quantum-chemical studies of higher excited states of merocyanine derivatives of azaazulene and indandione. A particular attention is paid to the analysis of fluorescence excitation anisotropy spectra of the mentioned compounds. The long-wave shift by ≈ 50 nm of a deep clear minimum in the fluorescence excitation anisotropy spectrum due to an elongation of the polymethine dye chromophore is established. Such shift is close in a value to the bathochromic shift of the first minimum in the anisotropy spectrum of symmetric ionic polymethine dyes, in which this minimum corresponds to the second electronic transition. The parallel spectral study and quantum-chemical calculations allowed us to correctly interpret the fluorescence excitation anisotropy spectra of merocyanines and relate the first clear minimum with the seventh electronic transition. The last resembles the second electronic transition between delocalized molecular orbitals (MO) in polymethine dyes.