Asymmetric adsorption of ethyliminium cation on kaolinite and l-homochirality of amino acids in proteins

Julg, André; Ozias, Yves

doi:10.1016/0166-1280(88)80110-6

Cited by 5 publications

(7 citation statements)

References 17 publications

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“…Experimentally a higher reactivity of the L optical isomer is observed. Degens et al ( ), Julg (1987 and Julg & Ozias (1988) interpreted the difference in reactivity of the two forms of optically active molecules in contact with the clay mineral by a "structural asymmetry" of the kaolinite crystal. In fact, there are two crystalline enantiomer forms of kaolinite.…”

Section: Discussionmentioning

confidence: 99%

Stereoselectivity of montmorillonite in the adsorption and deamination of some amino acids

Siffert

Naidja

1992

Clay miner.

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A B S T R A C T:Optical isomers deamination of L-and D-glutamic and aspartic amino acids and of their DL racemic mixtures has been achieved in the presence of Na-montmorillonite at pH = 6 and room temperature. The adsorption curves showed that the enantiomer adsorbed depends on the type of amino acid. Nevertheless, deamination reaction kinetics brought about a stereoselectivity of the clay mineral for the L-isomer and implicitly showed an unquestionable "structural chirality character" of the clay mineral.Since Bernal's hypothesis (1949) on the possible implication of clay minerals in the origin of life, several investigators (Paecht-Horowitz et al., 1970; Cairns-Smith, 1974, 1975 Lahav etal., 1978; Coyne etal., 1981; Coyne, 1985;Yamagishi, 1981 Yamagishi, , 1982Yamagishi, , 1983)have attempted to understand the action of clay minerals in the transformation and evolution of organic and bio-organic matter. Many investigators showed that the swelling clay minerals, especially montmorillonite, would be able to assume the role of a pseudo-enzyme (Mortland, 1984; Siffert & Naidja, 1987; Naidja & Siffert, 1989, 1990. The question which persists concerns the stereoselectivity of clay minerals in biochemical reactions, and in particular that raised by Degens et al. (1970) as to the cause of the L homochirality of amino acids in living organisms. It is necessary to note that organisms generally contain amino acids in their L-enantiomer form (Lavollay, 1980). Degens et al. (1970) reported a remarkable finding in connection with clay minerals, namely, that L,D-and D,L-aspartic acids in aqueous solution were polymerized at 90~ to differing extents by the catalytic action of kaolin. Thus the L-enantiomer was reported to polymerize to the extent of 25% and the D-isomer to the extent of only 3%. The authors concluded that an asymmetric synthesis of polypeptides had been accomplished on the clay surface and that polymers containing L-amino acids were formed preferentially to those containing D-enantiomers. A later report by Jackson (1971) purported to confirm these asymmetric polymerization findings, to show that the polymerization of aspartic acid failed to occur in the absence of kaolin as catalyst. Jackson also reported that L-phenylalanine was adsorbed by kaolinite to a higher extent than D-phenylalanine. In contrast to these observations, Bonner & Flores (1973) could find no evidence for the differential adsorption of D-versus L-phenylalanine by kaolin from either pH = 6 or pH = 2 solutions, using optical rotatory dispersion, gas chromatography and thin layer chromatography. However, optical rotatory dispersion measurements are unfortunately approximately within the experimental error of the observed rotations.9 1992 The Mineralogical Society

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Section: Discussionmentioning

confidence: 99%

Stereoselectivity of montmorillonite in the adsorption and deamination of some amino acids

Siffert

Naidja

1992

Clay miner.

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“…Amino acid molecules were also suggested to adsorb on the OH group of the edge of kaolinite by hydrogen bonding. 93,94 Nucleic acid bases also interact with the sodium cation through the O2 atom with NaÁ Á ÁO2 distance 2.29 A ˚in both, K(3o)Na-U and K(3o)Na-Th. The r and r 2 r values for the NaÁ Á ÁO2 bond are still positive but smaller than these values for HB1 which was found to be the strongest among all formed H-bonds in all calculated complexes.…”

Section: Interactions With Octahedral Surfacementioning

confidence: 99%

Adsorption of thymine and uracil on 1 : 1 clay mineral surfaces: comprehensive ab initio study on influence of sodium cation and water

Michalkova

Robinson

Leszczyński

2011

Phys. Chem. Chem. Phys.

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This computational study performed using the density functional theory shows that hydrated and non-hydrated tetrahedral and octahedral kaolinite mineral surfaces in the presence of a cation adsorb the nucleic acid bases thymine and uracil well. Differences in the structure and chemistry of specific clay mineral surfaces led to a variety of DNA bases adsorption mechanisms. The energetically most predisposed positions for an adsorbate molecule on the mineral surface were revealed. The target molecule binding with the surface can be characterized as physisorption, which occurs mainly due to a cation-molecular oxygen interaction, with hydrogen bonds providing an additional stabilization. The adsorption strength is proportional to the number of intermolecular interactions formed between the target molecule and the surface. From the Atoms in Molecules analysis and comparison of binding energy values of studied systems it is concluded that the sorption activity of kaolinite minerals for thymine and uracil depends on various factors, among which are the structure and accessibility of the organic compounds. The adsorption is governed mostly by the surface type, its properties and presence of cation, which cause a selective binding of the nucleobase. Adsorbate stabilization on the mineral surface increases only slightly with explicit addition of water. Comparison of activity of different studied kaolinite mineral models reveals the following order for stabilization: octahedral-Na-water > octahedral-Na > tetrahedral-Na > tetrahedral-Na-water. Further investigation of the electrostatic potentials helps understanding of the adsorption process and confirmation of the active sites on the kaolinite mineral surfaces. Based on the conclusions that clay mineral affinity for DNA and RNA bases can vary due to different structural and chemical properties of the surface, a hypothesis on possible role of clays in the origin of life was made.

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“…While we can only speculate on the nature of the surface(s) active in the described process, it is worth noting that the involvement of surfaces, such as that of TiO 2 (Senanayake and Idriss 2006), montmorrilonite (Kawamura and Ferris 1994;Ferris et al 1996) and pyrite (Huber and Wächtershäuser 1998), has been invoked in the formation of the first macromolecules essential to life, as well as in the formation of L-amino acids from RNA (Bailey 1998). Furthermore, it has been demonstrated that surfaces of kaolinite (Julg and Ozias 1988) and calcite (Hazen et al 2001) can exhibit preferential adsorption of specific amino acids or their precursors. Also, it has been shown (Weissbuch et al 2005) that racemic α-amino acids undergo spontaneous separation with the assistance of glycine crystals grown at the air/water interface.…”

Section: Abiotic Formation Of Enantiomerically Pure α-Ribopyranosementioning

confidence: 97%

A Possible Path to the RNA World: Enantioselective and Diastereoselective Purification of Ribose

Bielski¹,

Tencer²

2006

Orig Life Evol Biosph

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A theoretical mechanism resulting in the prebiotic appearance of enantiopure ribose, which would be needed for the origin of RNA and the "RNA world" is proposed. The mechanism simultaneously explains the emergence of biological homochirality and could answer the question of why nucleic acids are based on ribose rather than another sugar. Cleavage of certain non-chiral mineral crystals is known to lead to formation of chiral surfaces. In a chromatography-like process a mixture of racemic carbohydrates originating from the formose reaction is proposed to have been separated on such a chiral surface. Monosaccharides interact with surfaces through their hydroxyl groups, either by hydrogen bond formation or complex formation with metal ions. alpha-Ribopyranose, which has all hydroxyl groups on one side of the ring, is known to interact more strongly than other sugars with surfaces, as corroborated by certain chromatographic and electrophoresis data. A similar scenario leading to enantiopure ribose is separation on a flat, but not necessarily chiral surface in the presence of a strong electric field capable of orienting highly polar derivatives of sugars.

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Asymmetric adsorption of ethyliminium cation on kaolinite and l-homochirality of amino acids in proteins

Cited by 5 publications

References 17 publications

Stereoselectivity of montmorillonite in the adsorption and deamination of some amino acids

Stereoselectivity of montmorillonite in the adsorption and deamination of some amino acids

Adsorption of thymine and uracil on 1 : 1 clay mineral surfaces: comprehensive ab initio study on influence of sodium cation and water

A Possible Path to the RNA World: Enantioselective and Diastereoselective Purification of Ribose

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