On One Hand But Not The Other: The Challenge of the Origin and Survival of Homochirality in Prebiotic Chemistry

Frank, Patrick; Bonner, William A.; Zare, Richard N.

doi:10.1002/9783527612949.ch11

Cited by 38 publications

(32 citation statements)

References 171 publications

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“…The free amine was prepared according to Penney et al 16 and was further purified by column chromatography (silica gel, ethyl acetate:n-hexane:acetone ratio of 5:4.5:0.5). 1 18 ). The free amine was prepared according to Penney et al 16 16 The free amine was released from the hydrochloride salt by extraction with a triethylamine/water mixture and recrystallized from n-hexane.…”

Section: Methodsmentioning

confidence: 96%

Structure and Reactivity in Langmuir Films of Amphiphilic Alkyl and Thio-alkyl Esters of α-Amino Acids at the Air/Water Interface

et al. 2004

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The structure and reactivity of alkyl esters of several R-amino acids self-assembled at the air/water interface have been investigated as part of our studies on mechanisms that are possibly relevant for the generation of homochiral prebiotic peptides. Grazing incidence X-ray diffraction (GIXD) studies of monolayers of racemic and enantiopure alkyl esters and thio-esters of alanine on the water surface demonstrated that these racemates self-assemble in the form of mixed solid solutions, because of disorder of the headgroups of the two enantiomers (enantiomeric disorder) within the two-dimensional (2D) crystallites. Matrix-assisted laser-desorption ionization time-of-flight Mass Spectrum (MALDI-TOF MS) analysis of the products collected from the air/water interface indicated the formation of low-molecular-weight oligopeptides (primarily dimers) and, in the case of some of the thioesters, small quantities of trimers and tetramers. Mass spectrometric studies on the diastereoisomeric distribution of the oligopeptides, starting from deuterium enantio-labeled monomers, demonstrated binomial statistics, such as that in reactions occurring in an isotropic environment. The alkyl esters of phenylalanine and tyrosine did not form 2D crystallites at the air/water interface, and, upon polycondensation, they yielded only dipeptides. The enantiomeric disorder within the 2D crystallites of the monomers of the alkyl esters and thioesters of racemic serine was absent. Polycondensation of these esters, however, yielded only dipeptides and tripeptides and they were not investigated further. In contrast to previous reports, the present studies demonstrate that this reaction does not proceed beyond the dipeptide stage and, therefore, cannot be regarded as a plausible system for the generation of prebiotic peptides.

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Section: Methodsmentioning

confidence: 96%

Structure and Reactivity in Langmuir Films of Amphiphilic Alkyl and Thio-alkyl Esters of α-Amino Acids at the Air/Water Interface

et al. 2004

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“…However, modern theoretical studies [11][12][13][14][15][16][17][18][19][20][21][22][23]26,28,30,31,33,[36][37][38][39][40][41]43,44,46] have claimed that an image and its mirror molecule are no longer enantiomers due to an energy inequality induced by the existence of PV-WNC. Due to a parity-violating energy shift (PVES) of the electronic binding energy with a positive value, +E PV , for the image molecule and a PVES with a negative value, -E PV , for the mirror image molecule, or vice versa, PVES makes the pair become a diastereomer, exhibiting subtle differences in physical properties and chemical processes.…”

Section: Introductionmentioning

confidence: 99%

Mirror Symmetry Breaking in Helical Polysilanes: Preference between Left and Right of Chemical and Physical Origin

Fujiki

2010

Symmetry

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Abstract:From elemental particles to human beings, matter is dissymmetric with respect to mirror symmetry. In 1860, Pasteur conjectured that biomolecular handednesshomochirality-may originate from certain inherent dissymmetric forces existing in the universe. Kipping, a pioneer of organosilicon chemistry, was interested in the handedness of sodium chlorate during his early research life. Since Kipping first synthesized several Si-Si bonded oligomers bearing phenyl groups, Si-Si bonded high polymers carrying various organic groups-polysilanes-can be prepared by sodium-mediated condensation of the corresponding organodichlorosilanes. Among these polysilanes, optically active helical polysilanes with enantiomeric pairs of organic side groups may be used for testing the mirror symmetry-breaking hypothesis by weak neutral current (WNC) origin in the realm of chemistry and material science. Several theoretical studies have predicted that WNC-existing chiral molecules with stereogenic centers and/or stereogenic bonds allow for distinguishing between image and mirror image molecules. Based on several amplification mechanisms, theorists claimed that minute differences, though still very subtle, may be detectable by precise spectroscopic and physicochemical measurements if proper chiral molecular pairs were employed. The present paper reports comprehensively an inequality between six pairs of helical polysilane high polymers, presumably, detectable by (chir)optical and achiral 29 Si-/ 13 C-NMR spectra, and viscometric measurements.

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“…The question of how homochirality of biomolecules evolved from an achiral prebiotic environment has intrigued scientists for a long time [238][239][240]. This led to numerous suggestions and a quest for finding the appropriate amplification mechanism for symmetry-breaking scenarios at various stages of the emergence of life [241][242][243][244][245].…”

Section: Diastereomers and Diastereomeric Recognitionmentioning

confidence: 99%

Molecular chirality at surfaces

Ernst

2012

Physica Status Solidi (b)

223

264

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With the adsorption of larger molecules being increasingly tackled by surface scientists, the aspect of chirality often plays a role. This paper gives a topical review of molecular chirality at surfaces and gives a phenomenological overview of different aspects of adsorption and self‐assembly of chiral and prochiral molecules and the principles of mirror‐symmetry breaking at a surface. After a brief introduction into the history of molecular chirality and the important role it played for understanding the spatial structure of molecules, definitions of chirality are presented. Topics treated here are principle ways to create single chiral adsorbates, chiral ensembles, and monolayers by achiral molecules, adsorption of intrinsically chiral molecules at achiral and chiral surfaces, long‐range symmetry breaking in two‐dimensional (2D) crystals due to additional chiral bias, chiral restructuring of solid surfaces under the influence of chiral molecules, switching the handedness of adsorbates, and chirality at the liquid/air interface. An outlook onto further potential research directions and recommendations for further reading, including nonsurface‐related sources of chiral topics completes this paper.

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On One Hand But Not The Other: The Challenge of the Origin and Survival of Homochirality in Prebiotic Chemistry

Cited by 38 publications

References 171 publications

Structure and Reactivity in Langmuir Films of Amphiphilic Alkyl and Thio-alkyl Esters of α-Amino Acids at the Air/Water Interface

Structure and Reactivity in Langmuir Films of Amphiphilic Alkyl and Thio-alkyl Esters of α-Amino Acids at the Air/Water Interface

Mirror Symmetry Breaking in Helical Polysilanes: Preference between Left and Right of Chemical and Physical Origin

Molecular chirality at surfaces

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