Abstract
Chirality is the property of a molecule to be nonsuperimposable with its mirror image. In biology, basically all chiral molecules exist in only one mirror-image form, or enantiomer, a phenomenon called biological homochirality. For example, chiral amino acids occur nearly exclusively in the l-form and carbohydrates in the d-form. In contrast, chiral molecules on the early Earth should have been racemic, i.e., consisting of equal amounts of both enantiomers, before life came into existence. The emergence of biological homochirality is therefore directly linked with the origin of life but remains an intriguing and unanswered puzzle for scientists. To chemists, it poses a challenge to create model systems for the emergence of homochirality from a racemic state. This chapter gives an overview of such chemical models as well as other experiments and observations that might explain how biological homochirality was achieved.
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Amedjkouh M, Brandberg M (2008) Asymmetric autocatalytic Mannich reaction in the presence of water and its implication in prebiotic chemistry. Chem Commun 44:3043–3045
Ávalos M, Babiano R, Cintas P, Jiménez JL, Palacios JC (2010) Chirality and life. Tetrahedron Asymmetry 21:1030–1040
Bailey J, Chrysostomou A, Hough JH, Gledhill TM, McCall A, Clark S, Ménard F, Tamura M (1998) Circular polarization in star-formation regions: implications for biomolecular homochirality. Science 281:672–674
Barron LD (2008) Chirality and life. Space Sci Rev 135:187–201
Blackmond DG (2004) Asymmetric autocatalysis and its implications for the origin of homochirality. Proc Natl Acad Sci USA 101:5732–5736
Blackmond DG (2007) “Chiral amnesia” as a driving force for solid-phase homochirality. Chem Eur J 13:3290–3295
Blackmond DG, Klussmann M (2007) Spoilt for choice: assessing phase behavior models for the evolution of homochirality. Chem Commun 43:3990–3996
Blackmond DG, McMillan CR, Ramdeehul S, Schorm A, Brown JM (2001) Origins of asymmetric amplification in autocatalytic alkylzinc additions. J Am Chem Soc 123:10103–10104
Blair NE, Bonner WA (1981) A model for the enantiomeric enrichment of polypeptides on the primitive Earth. Orig Life Evol Biosph 11:331–335
Bonner WA (1991) The origin and amplification of biomolecular chirality. Orig Life Evol Biosph 21:59–111
Bonner WA, Kavasmaneck PR, Martin FS, Flores JJ (1974) Asymmetric adsorption of alanine by quartz. Science 186:143–144
Brack A (2007) From interstellar amino acids to prebiotic catalytic peptides: a review. Chem Biodivers 4:665–679
Breslow R (2011) A likely possible origin of homochirality in amino acids and sugars on prebiotic earth. Tetrahedron Lett 52:2028–2032
Budin I, Szostak JW (2010) Expanding roles for diverse physical phenomena during the origin of life. Annu Rev Biophys 39:245–263
Cintas P (2002) Chirality of living systems: a helping hand from crystals and oligopeptides. Angew Chem Int Ed 41:1139–1145
Córdova A, Zou W, Dziedzic P, Ibrahem I, Reyes E, Xu Y (2006) Direct asymmetric intermolecular aldol reactions catalyzed by amino acids and small peptides. Chem Eur J 12:5383–5397
Crossley R (1992) The relevance of chirality to the study of biological activity. Tetrahedron 48:8155–8178
Fletcher SP, Jagt RBC, Feringa BL (2007) An astrophysically-relevant mechanism for amino acid enantiomer enrichment. Chem Commun 43:2578–2580
Flores JJ, Bonner WA, Massey GA (1977) Asymmetric photolysis of (RS)-leucine with circularly polarized ultraviolet light. J Am Chem Soc 99:3622–3625
Frank FC (1953) On spontaneous asymmetric synthesis. Biochim Biophys Acta 11:459–463
Fuß W (2009) Does life originate from a single molecule? Chirality 21:299–304
Green M, Jain V (2010) Homochirality in life: two equal runners, one tripped. Orig Life Evol Biosph 40:111–118
Green MM, Park J-W, Sato T, Teramoto A, Lifson S, Selinger RLB, Selinger JV (1999) The macromolecular route to chiral amplification. Angew Chem Int Ed 38:3138–3154
Griesbeck AG, Meierhenrich UJ (2002) Asymmetric photochemistry and photochirogenesis. Angew Chem Int Ed 41:3147–3154
Hazen RM, Filley TR, Goodfriend GA (2001) Selective adsorption of L- and D-amino acids on calcite: implications for biochemical homochirality. Proc Natl Acad Sci USA 98:5487–5490
Hitz TH, Luisi PL (2004) Spontaneous onset of homochirality in oligopeptide chains generated in the polymerization of N-carboxyanhydride amino acids in water. Orig Life Evol Biosph 34:93–110
Jacques J, Collet A, Wilen SH (1981) Enantiomers, racemates and resolution. Wiley, New York
Kawasaki T, Matsumura Y, Tsutsumi T, Suzuki K, Ito M, Soai K (2009) Asymmetric autocatalysis triggered by carbon isotope (13C/12C) chirality. Science 324:492–495
Klussmann M, Iwamura H, Mathew SP, Wells DH Jr, Pandya U, Armstrong A, Blackmond DG (2006a) Thermodynamic control of asymmetric amplification in amino acid catalysis. Nature 441:621–623
Klussmann M, White AJP, Armstrong A, Blackmond DG (2006b) Rationalisation and prediction of solution enantiomeric excess in ternary phase systems. Angew Chem Int Ed 45:7985–7989
Kondepudi DK, Kaufman RJ, Singh N (1990) Chiral symmetry breaking in sodium chlorate crystallization. Science 250:975–976
Kricheldorf HR (2006) Polypeptides and 100 years of chemistry of a-amino acid N-carboxyanhydrides. Angew Chem Int Ed 45:5752–5784
Lahav M, Weissbuch I, Shavit E, Reiner C, Nicholson GJ, Schurig V (2006) Parity violating energetic difference and enantiomorphous crystals-caveats; reinvestigation of tyrosine crystallization. Orig Life Evol Biosph 36:151–170
Leitereg TJ, Guadagni DG, Harris J, Mon TR, Teranishi R (1971) Evidence for the difference between the odors of the optical isomers (+)- and (-)-carvone. Nature 230:455–456
Lente G (2006) Stochastic analysis of the parity-violating energy differences between enantiomers and its implications for the origin of biological chirality. J Phys Chem A 110:12711–12713
Luisi PL (2006) The emergence of life: from chemical origins to synthetic biology. Cambridge University Press, Cambridge
Mauksch M, Tsogoeva SB, Martynova IM, Wei S (2007) Evidence of asymmetric autocatalysis in organocatalytic reactions. Angew Chem Int Ed 46:393–396
Meinert C, Filippi JJ, Nahon L, Hoffmann SV, d’Hendecourt L, de Marcellus P, Bredehöft JH, Thiemann WHP, Meierhenrich UJ (2010) Photochirogenesis: photochemical models on the origin of biomolecular homochirality. Symmetry 2:1055–1080
Morowitz HJ (1969) A mechanism for the amplification of fluctuations in racemic mixtures. J Theor Biol 25:491–494
Mukherjee S, Yang JW, Hoffmann S, List B (2007) Asymmetric enamine catalysis. Chem Rev 107:5471–5569
Noorduin WL, Izumi T, Millemaggi A, Leeman M, Meekes H, Enckevort WJPV, Kellogg RM, Kaptein B, Vlieg E, Blackmond DG (2008) Emergence of a single solid chiral state from a nearly racemic amino acid derivative. J Am Chem Soc 130:1158–1159
Orgel LE (2004) Prebiotic chemistry and the origin of the RNA world. Crit Rev Biochem Mol Biol 39:99–123
Pasek M, Lauretta D (2008) Extraterrestrial flux of potentially prebiotic C, N, and P to the early Earth. Orig Life Evol Biosph 38:5–21
Patzke V, Kiedrowski GV (2007) Self replicating systems. ARKIVOC 293–310
Perry RH, Wu C, Nefliu M, Cooks RG (2007) Serine sublimes with spontaneous chiral amplification. Chem Commun 43:1071–1073
Pizzarello S, Cronin JR (2000) Non-racemic amino acids in the Murray and Murchison meteorites. Geochim Cosmochim Acta 64:329–338
Pizzarello S, Weber AL (2004) Prebiotic amino acids as asymmetric catalysts. Science 303:1151
Pizzarello S, Zolensky M, Turk KA (2003) Nonracemic isovaline in the Murchison meteorite: chiral distribution and mineral association. Geochim Cosmochim Acta 67:1589–1595
Pizzarello S, Huang Y, Fuller M (2004) The carbon isotopic distribution of Murchison amino acids. Geochim Cosmochim Acta 68:4963–4969
Podlech J (2001) Origin of organic molecules and biomolecular homochirality. Cell Mol Life Sci 58:44–60
Robertson A, Sinclair AJ, Philp D (2000) Minimal self-replicating systems. Chem Soc Rev 29:141–152
Rubinstein I, Eliash R, Bolbach G, Weissbuch I, Lahav M (2007) Racemic beta sheets in biochirogenesis. Angew Chem Int Ed 46:3710–3713
Saghatelian A, Yokobayashi Y, Soltani K, Ghadiri MR (2001) A chiroselective peptide replicator. Nature 409:797–801
Sato I, Omiya D, Saito T, Soai K (2000) Highly enantioselective synthesis induced by chiral primary alcohols due to deuterium substitution. J Am Chem Soc 122:11739–11740
Sato I, Yamashima R, Kadowaki K, Yamamoto J, Shibata T, Soai K (2001) Asymmetric induction by helical hydrocarbons: [6]- and [5]helicenes. Angew Chem Int Ed 40:1096–1098
Satyanarayana T, Abraham S, Kagan HB (2009) Nonlinear effects in asymmetric catalysis. Angew Chem Int Ed 48:456–494
Siegel JS (1998) Homochiral imperative of molecular evolution. Chirality 10:24–27
Soai K, Shibata T, Morioka H, Choji K (1995) Asymmetric autocatalysis and amplification of enantiomeric excess of a chiral molecule. Nature 378:767–768
Soai K, Osanai S, Kadowaki K, Yonekubo S, Shibata T, Sato I (1999) d- and l-quartz-promoted highly enantioselective synthesis of a chiral organic compound. J Am Chem Soc 121:11235–11236
Soai K, Shibata T, Sato I (2004) Discovery and development of asymmetric autocatalysis. Bull Chem Soc Jpn 77:1063–1073
Stoeffler C, Darquie B, Shelkovnikov A, Daussy C, Amy-Klein A, Chardonnet C, Guy L, Crassous J, Huet TR, Soulard P, Asselin P (2011) High resolution spectroscopy of methyltrioxorhenium: towards the observation of parity violation in chiral molecules. Phys Chem Chem Phys 13:854–863
Strasdeit H (2005) New studies on the Murchison meteorite shed light on the pre-RNA world. Chembiochem 6:801–803
Triggle DJ (1997) Stereoselectivity of drug action. Drug Discov Today 2:138–147
Viedma C (2005) Chiral symmetry breaking during crystallization: complete chiral purity induced by nonlinear autocatalysis and recycling. Phys Rev Lett 94:065504
Viedma C, Ortiz JE, de Torres T, Izumi T, Blackmond DG (2008) Evolution of solid phase homochirality for a proteinogenic amino acid. J Am Chem Soc 130:15274–15275
Wang X, Zhang Y, Tan H, Wang Y, Han P, Wang DZ (2010) Enantioselective organocatalytic Mannich reactions with autocatalysts and their mimics. J Org Chem 75:2403–2406
Weber AL, Pizzarello S (2006) The peptide-catalyzed stereospecific synthesis of tetroses: a possible model for prebiotic molecular evolution. Proc Natl Acad Sci USA 103:12713–12717
Weissbuch I, Leiserowitz L, Lahav M (2005) Stochastic “mirror symmetry breaking” via self-assembly, reactivity and amplification of chirality: relevance to abiotic conditions. Top Curr Chem 259:123–165
Welch CJ (2001) Formation of highly enantioenriched microenvironments by stochastic sorting of conglomerate crystals: a plausible mechanism for generation of enantioenrichment on the prebiotic earth. Chirality 13:425–427
Wesendrup R, Laerdahl JK, Compton RN, Schwerdtfeger P (2003) Biomolecular homochirality and electroweak interactions. I. The Yamagata hypothesis. J Phys Chem A 107:6668–6673
Wu CS, Ambler E, Hayward RW, Hoppes DD, Hudson RP (1957) Experimental test of parity conservation in beta decay. Phys Rev 105:1413–1415
Yamagata Y (1966) A hypothesis for the asymmetric appearance of biomolecules on earth. J Theor Biol 11:495–498
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Klussmann, M. (2012). Chemical Models for the Origin of Biological Homochirality. In: Seckbach, J. (eds) Genesis - In The Beginning. Cellular Origin, Life in Extreme Habitats and Astrobiology, vol 22. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-2941-4_26
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