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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., (Copyright © 2014 Wiley Periodicals, Inc.)

Amino acids are the fundamental building blocks of proteins, the biomolecules that provide cellular structure and function in all living organisms. A majority of amino acids utilized within living systems possess pre-specified orientation geometry (chirality); however the original source for this specific orientation remains uncertain. In order to trace the chemical evolution of life, an appreciation of the synthetic and evolutional origins of the first chiral amino acids must first be gained. Given that the amino acids in our universe are likely to have been synthesized in molecular clouds in interstellar space, it is necessary to understand where and how the first synthesis might have occurred. The asymmetry of the original amino acid synthesis was probably the result of exposure to chiral photons in the form of circularly polarized light (CPL), which has been detected in interstellar molecular clouds. This chirality transfer event, from photons to amino acids, has been successfully recreated experimentally and is likely a combination of both asymmetric synthesis and enantioselective photolysis. A series of innovative studies have reported successful simulation of these environments and afforded production of chiral amino acids under realistic circumstellar and interstellar conditions: irradiation of interstellar ice analogues (CO, CO2, NH3, CH3OH, and H2O) with circularly polarized ultraviolet photons at low temperatures does result in enantiomer enriched amino acid structures (up to 1.3% ee). This topical review summarizes current knowledge and recent discoveries about the simulated interstellar environments within which amino acids were probably formed. A synopsis of the COSAC experiment onboard the ESA cometary mission ROSETTA concludes this review: the ROSETTA mission will soft-land on the nucleus of the comet 67P/Churyumov-Gerasimenko in November 2014, anticipating the first in situ detection of asymmetric organic molecules in cometary ices.

The primordial appearance of chiral amino acids was an essential component of the asymmetric evolution of life on Earth. In this tutorial review we will explore the original life-generating, symmetry-breaking event and summarise recent thoughts on the origin of enantiomeric excess in the universe. We will then highlight the transfer of asymmetry from chiral photons to racemic amino acids and elucidate current experimental data on the photochemical synthesis of amino and diamino acid structures in simulated interstellar and circumstellar ice environments. The chirality inherent within actual interstellar (cometary) ice environments will be considered in this discussion: in 2014 the Rosetta Lander Philae onboard the Rosetta space probe is planned to detach from the orbiter and soft-land on the surface of the nucleus of comet 67P/Churyumov-Gerasimenko. It is equipped for the in situ enantioselective analysis of chiral prebiotic organic species in cometary ices. The scientific design of this mission will therefore be presented in the context of analysing the formation of amino acid structures within interstellar ice analogues as a means towards furthering understanding of the origin of asymmetric biological molecules.

Circularly polarized light (CPL) is known to be a true chiral entity capable of generating absolute molecular asymmetry. However, the degree of inducible optical activity depends on the λ of the incident CPL. Exposure of amorphous films of rac-alanine to tunable CPL led to enantiomeric excesses ( ee) which not only follow the helicity but also the energy of driving electromagnetic radiation. Postirradiation analyses using enantioselective multidimensional GC revealed energy-controlled ee values of up to 4.2 %, which correlate with theoretical predictions based on newly recorded anisotropy spectra g( λ). The tunability of asymmetric photochemical induction implies that both magnitude and sign can be fully controlled by CPL. Such stereocontrol provides novel insights into the wavelength and polarization dependence of asymmetric photochemical reactions and are highly relevant for absolute asymmetric molecular synthesis and for understanding the origins of homochirality in living matter. [ABSTRACT FROM AUTHOR]

A correction to an article related to the chirality and synthesis of amino acids under interstellar conditions that was published in the 2013 issue of the "Topics in Current Chemistry" is presented.