Abstract
Many chemical and physical systems can occur in two forms distinguished solely by being mirror images of each other. This phenomenon, known as chirality, is important in biochemistry, where reactions involving chiral molecules often require the participation of one specific enantiomer (mirror image) of the two possible ones. In fact, terrestrial life utilizes only the L enantiomers of amino acids, a pattern that is known as the ‘homochirality of life’ and which has stimulated long-standing efforts to understand its origin1. Reactions can proceed enantioselectively if chiral reactants or catalysts are involved, or if some external chiral influence is present2. But because chiral reactants and catalysts themselves require an enantioselective production process, efforts to understand the homochirality of life have focused on external chiral influences. One such external influence is circularly polarized light, which can influence the chirality of photochemical reaction products2,13,14. Because natural optical activity, which occurs exclusively in media lacking mirror symmetry, and magnetic optical activity, which can occur in all media and is induced by longitudinal magnetic fields, both cause polarization rotation of light, the potential for magnetically induced enantioselectivity in chemical reactions has been investigated, but no convincing demonstrations of such an effect have been found2,3,4. Here we show experimentally that magnetochiral anisotropy—an effect linking chirality and magnetism5,6,7—can give rise to an enantiomeric excess in a photochemical reaction driven by unpolarized light in a parallel magnetic field, which suggests that this effect may have played a role in the origin of the homochirality of life.
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References
Cline, D. B. (ed.) Physical Origin of Homochirality in Life (American Institute of Physics, New York, 1996).
Avalos, M. et al. Absolute asymmetric synthesis under physical fields: Facts and fictions. Chem. Rev. 98, 2391– 2404 (1998).
Mason, S. F. in Circular Dichroism (eds Nakanishi, K., Berova, N. & Woody, R. W.) Ch. 2 (VCH, New York, 1994).
Bonner, W. A. Chirality and life. Orig. Life Evol. Biosphere 25, 175–190 (1995).
Rikken, G. L. J. A. & Raupach, E. Observation of magneto-chiral dichroism. Nature 390, 493 –494 (1997).
Kleindienst, P. & Wagnière, G. Interferometric detection of magnetochiral birefringence. Chem. Phys. Lett. 288, 89–97 (1998).
Rikken, G. L. J. A. & Raupach, E. Pure and cascaded magnetochiral anisotropy in optical absorption. Phys. Rev. E 58, 5081–5084 (1998).
Barron, L. D. True and false chirality and absolute asymmetric synthesis. J. Am. Chem. Soc. 108, 5539–5542 (1986).
Barron, L. D. Can a magnetic field induce absolute asymmetric synthesis? Science 266, 1491–1492 ( 1994).
Portigal, D. L. & Burstein, E. Magneto-spatial dispersion effects on the propagation of electromagnetic radiation in crystals. J. Phys. Chem. Solids 32, 603– 608 (1971).
Baranova, N. B., Bogdanov, Yu. V. & Zeldovich, B. Ya. Electrical analog of the Faraday effect and other new optical effects in liquids. Opt. Commun. 22, 243–247 (1977).
Baranova, N. B. & Zeldovich, B. Ya. Theory of a new linear magnetorefractive effect in liquids. Mol. Phys. 38, 1085–1098 (1979).
Rau, H. Asymmetric photochemistry in solution. Chem. Rev. 83, 535–547 (1983).
Inoue, Y. Asymmetric photochemical reactions in solution. Chem. Rev. 92, 741–770 (1992).
Barron, L. D. & Vrbancich, J. Magneto-chiral birefringence and dichroism. Mol. Phys. 51, 715– 730 (1984).
Stevenson, K. L. & Verdieck, J. F. Partial photoresolution II. Application to some chromium complexes. Mol. Photochem. 1, 271–288 (1969).
McCaffery, A. J., Mason, S. F. & Ballard, R. E. Optical rotatory power of coordination compounds. Part III The absolute configurations of trigonal metal complexes. J. Chem. Soc. 2883–2892 ( 1965).
McCaffery, A. J., Stephens, P. J. & Schatz, P. N. The magnetic optical activity of d → d transitions. Octahedral chromium(III), cobalt(III), nickel(II) and manganese(II) complexes. Inorg. Chem. 6, 1614–1625 (1967).
Pracejus, H. Asymmetrische Synthesen. Fortschr. Chem. Forsch. 8, 493–553 (1967).
Bernstein, W. J. The attempted asymmetric synthesis of helicenes by photolysis under magnetic field. Thesis, Lawrence Berkeley Labs (1972).
Teutsch, H. Zur Enstehung optischer Aktivität in der Biosphäre: Ausgewählte Photoreaktionen als asymmetrischen Synthesen. Thesis, Univ. Bremen (1988).
Wagnière, G. & Meier, A. Difference in the absorption coefficient of enantiomers for arbitrarily polarized light in a magnetic field—A possible source of chirality in molecular evolution. Experientia 39, 1090–1091 (1983).
Engel, M. H. & Macko, S. A. Isotopic evidence for extraterrestial non-racemic amino acids in the Murchison meteorite. Nature 389, 265–268 (1997).
Bailey, J. et al. Circular polarization in star-formation regions: Implications for biomolecular homochirality. Science 281, 672–674 (1998).
Lyne, A. G. Origins of the magnetic fields of neutron stars. Nature 308, 605–606 (1984).
Acknowledgements
We thank H. Krath for technical assistance; P. Wyder, G. Martinez and B. van Tiggelen for comments on the manuscript; W. A. Bonner for providing important information; L. Barron for discussions; and B. Malezieux for synthesizing the pure enantiomers. The Grenoble High Magnetic Field Laboratory is a “laboratoire conventionné aux universités UJF et INP de Grenoble”.
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Rikken, G., Raupach, E. Enantioselective magnetochiral photochemistry. Nature 405, 932–935 (2000). https://doi.org/10.1038/35016043
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DOI: https://doi.org/10.1038/35016043
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