Chiral Symmetry Breaking During the Self-Assembly of Monolayers from Achiral Purine Molecules

Sowerby, Stephen J.; Heckl, Wolfgang M.; Petersen, George B.

doi:10.1007/pl00006101

Cited by 41 publications

(94 citation statements)

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“…In some cases, adsorbed molecules have been found to organize into periodic two-dimensional surface structure-structures that might have played a role in prebiotic chemical evolution. Sowerby et al (1996Sowerby et al ( , 1998aSowerby et al ( , 1998bSowerby et al ( , 2002 used scanning tunneling microscopy to document structures of self-assembled monolayers of adenine and guanine on graphite (C) and molybdenite (MoS 2 ), Kühnle et al (2002) imaged individual cysteine dimers adsorbed on gold, and Uchihashi et al (1999) observed adenine adsorption on graphite with noncontact AFM. AFM studies and molecular calculations also suggest that amino acids can adsorb selectively along linear surface steps of calcite (Orme et al 2001;de Yoreo and Dove 2004), perhaps providing an alignment conducive to homochiral polymerization .…”

Section: Molecular Organizationmentioning

confidence: 99%

Mineral Surfaces, Geochemical Complexities, and the Origins of Life

Hazen

Sverjensky²

2010

Cold Spring Harbor Perspectives in Biology

283

237

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Crystalline surfaces of common rock-forming minerals are likely to have played several important roles in life's geochemical origins. Transition metal sulfides and oxides promote a variety of organic reactions, including nitrogen reduction, hydroformylation, amination, and Fischer-Tropsch-type synthesis. Fine-grained clay minerals and hydroxides facilitate lipid self-organization and condensation polymerization reactions, notably of RNA monomers. Surfaces of common rock-forming oxides, silicates, and carbonates select and concentrate specific amino acids, sugars, and other molecular species, while potentially enhancing their thermal stabilities. Chiral surfaces of these minerals also have been shown to separate left-and right-handed molecules. Thus, mineral surfaces may have contributed centrally to the linked prebiotic problems of containment and organization by promoting the transition from a dilute prebiotic "soup" to highly ordered local domains of key biomolecules.

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Section: Molecular Organizationmentioning

confidence: 99%

Mineral Surfaces, Geochemical Complexities, and the Origins of Life

Hazen

Sverjensky²

2010

Cold Spring Harbor Perspectives in Biology

283

237

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“…This includes, in particular, the possibility that chiral layers are formed from achiral, racemic, and chiral species. [12][13][14][15] In some cases, indications of spontaneous chiral segregation of racemic films have been reported. [16][17][18][19] When the substrate atomic order is affected, even chiral restructuring may occur.…”

Section: Introductionmentioning

confidence: 99%

Stereochemical Effects in Supramolecular Self-Assembly at Surfaces: 1-D versus 2-D Enantiomorphic Ordering for PVBA and PEBA on Ag(111)

et al. 2002

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Abstract:We present investigations on noncovalent bonding and supramolecular self-assembly of two related molecular building blocks at a noble metal surface: 4-[trans-2-(pyrid-4-yl-vinyl)]benzoic acid (PVBA) and 4-[(pyrid-4-yl-ethynyl)]benzoic acid (PEBA). These rigid, rodlike molecules comprising the same complementary moieties for hydrogen bond formation are comparable in shape and size. For PVBA, the ethenylene moiety accounts for two-dimensional (2-D) chirality upon confinement to a surface; PEBA is linear and thus 2-D achiral. Molecular films were deposited on a Ag(111) surface by organic molecular beam epitaxy and characterized by scanning tunneling microscopy. At low temperatures (around 150 K), both species form irregular networks of flat lying molecules linked via their endgroups in a diffusion-limited aggregation process. In the absence of kinetic limitations (adsorption or annealing at room temperature), hydrogen-bonded supramolecular assemblies form which are markedly different. With PVBA, enantiomorphic twin chains in two mirror-symmetric species running along a high-symmetry direction of the substrate lattice form by diastereoselective self-assembly of one enantiomer. The chirality signature is strictly correlated between neighboring twin chains. Enantiopure one-dimensional (1-D) supramolecular nanogratings with tunable periodicity evolve at intermediate coverages, reflecting chiral resolution in micrometer domains. In contrast, PEBA assembles in 2-D hydrogen-bonded islands, which are enantiomorphic because of the orientation of the supramolecular arrangements along low-symmetry directions of the substrate. Thus, for PVBA, chiral molecules form 1-D enantiomorphic supramolecular structures because of mesoscopic resolution of a 2-D chiral species, whereas with PEBA, the packing of an achiral species causes 2-D enantiomorphic arrangements. Model simulations of supramolecular ordering provide a deeper understanding of the stability of these systems.

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“…The purine and pyrimidine bases adsorb spontaneously from aqueous media onto inorganic solids and have been observed on the surfaces of graphite (17)(18)(19)(20)(21), MoS 2 (15,(18)(19)(20)(21), crystalline gold (22), and clays (23,24). Scanning probe microscopy (SPM) studies have shown that the bases are planar-arranged on these surfaces like jigsaw puzzle pieces.…”

mentioning

confidence: 99%

“…Scanning probe microscopy (SPM) studies have shown that the bases are planar-arranged on these surfaces like jigsaw puzzle pieces. They are stabilized by van der Waals interactions with the underlying surface and by hydrogen bonds between adjacent molecules (15,(18)(19)(20)(21)25), a configuration originally postulated on the basis of thermodynamic measurements made at the mercury-water interface (26). The hydrogen bonds between the bases are drawn from a discrete set of possible interactions including those of Watson-Crick pairing found in nucleic acids (15).…”

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confidence: 99%

Differential adsorption of nucleic acid bases: Relevance to the origin of life

Sowerby

Cohn

Heckl

et al. 2001

Proc. Natl. Acad. Sci. U.S.A.

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The adsorption of organic molecules onto the surfaces of inorganic solids has long been considered a process relevant to the origin of life. We have determined the equilibrium adsorption isotherms for the nucleic acid purine and pyrimidine bases dissolved in water on the surface of crystalline graphite. The markedly different adsorption behavior of the bases describes an elutropic series: guanine > adenine > hypoxanthine > thymine > cytosine > uracil. We propose that such differential properties were relevant to the prebiotic chemistry of the bases and may have influenced the composition of the primordial genetic architecture.T he purine and pyrimidine coding elements of nucleic acids are products of putative prebiotic chemistries that invoke cyanide (1, 2) and have been synthesized in reactions that also yield amino acids (3). The prebiotic availability of these compounds supports the RNA World Hypothesis (4) for the origin of life, which presupposes that the first living system was a polymer(s) of catalytic RNA capable of self-replication that subsequently evolved the ability to encode more versatile peptide catalysts. RNA can act as both information carrier and catalyst (5) and, in the laboratory, can be coerced into different catalytic functions through directed Darwinian evolution (6).Despite these properties, there are severe difficulties with the de novo appearance of RNA, and, even in the most optimistic scenario, information-bearing molecule(s) capable of selfreplication must have first formed fortuitously from an astronomical range of possibilities (7). Although RNA-mediated catalysis and the nonenzymic polymerization of nucleotides (8,9) are well demonstrated, nucleic acid structure incorporates carbohydrate moieties. Formaldehyde, a seemingly ubiquitous compound, is regarded as the most plausible precursor of carbohydrates; however, cyanohydrin (glyconitrile) is the major highly stable product of reactions between formaldehyde and cyanide, withdrawing the latter from being a putative source of bases and amino acids (10). The recovery of nonbiogenic amino acids and bases from extraterrestrial debris (11) suggests the spatial-temporal separation of formaldehyde and cyanide. Life may have been initiated in the absence of carbohydrates, and it has been proposed that modern biology was preceded by a non-nucleic acid informational architecture (12, 13).Aperiodicity is required to convey information (14), and it has been demonstrated that aperiodic structures can self-assemble from aqueous mixtures of purine and pyrimidine bases adsorbed onto the surface of an uncharged inorganic crystalline mineral (15). The spontaneous formation of such structures suggests the existence of an organic, nonpolymeric informational architecture that may have had relevance to the origin of life.The adsorption of organic molecules onto inorganic solids has long been considered a relevant prebiotic process (16). The purine and pyrimidine bases adsorb spontaneously from aqueous media onto inorganic solids and have been observed o...

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Chiral Symmetry Breaking During the Self-Assembly of Monolayers from Achiral Purine Molecules

Cited by 41 publications

References 0 publications

Mineral Surfaces, Geochemical Complexities, and the Origins of Life

Mineral Surfaces, Geochemical Complexities, and the Origins of Life

Stereochemical Effects in Supramolecular Self-Assembly at Surfaces: 1-D versus 2-D Enantiomorphic Ordering for PVBA and PEBA on Ag(111)

Differential adsorption of nucleic acid bases: Relevance to the origin of life

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