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Interactions of amino acids and aminoxazole derivatives: Cocrystal formation and prebiotic implications enabled by computational analysis

Interactions of amino acids and aminoxazole derivatives: Cocrystal formation and prebiotic implications enabled by computational analysis
Interactions of amino acids and aminoxazole derivatives: Cocrystal formation and prebiotic implications enabled by computational analysis
In line with the postulated intermediacy of aminoxazoles derived from small sugars toward the direct assembly of nucleoside precursors, we show here a potential prebiotic scenario where aminoxazolines might have also played further roles as complexing and/or sequestering agents of other primeval blocks, namely amino acids. To this end, a bis-aminoxazoline derivative, generated from dihydroxyacetone and cyanamide, gives rise to stable co-crystal forms with dicarboxylic amino acids (Asp and Glu), while ionic interactions owing to proton transfer are inferred from spectroscopic data in aqueous solution. The structure of a 1:2 aminoxazoline: aspartic acid complex, discussed in detail, was elucidated by X-ray diffractometry. Optimized geometries of such ionic structures with bulk aqueous solvation were assessed by DFT calculations, which disclose preferential arrangements that validate the experimental data. Peripherally, we were able to detect in a few cases amino acid dimerization (i.e. dipeptide formation) after prolonged incubation with the bis-aminoxazole derivative. A mechanistic simulation aided by computation provides some predictive conclusions for future explorations and catalytic design.
Prebiotic chemistry, Amino acids, Aminoxazole chemistry, Reaction mechanism, Dipeptide
0169-6149
1-23
Lavado, Nieves
7cbccc77-1007-4286-b91a-336f88da5fa1
García de la Concepción, Juan
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Babiano, Reyes
b7ffd91c-bacd-4372-ab99-fc30ac2450ae
Cintas, Pedro
29979233-8382-47a8-bde7-1faf4869308c
Light, Mark
cf57314e-6856-491b-a8d2-2dffc452e161
Lavado, Nieves
7cbccc77-1007-4286-b91a-336f88da5fa1
García de la Concepción, Juan
d8ca3ced-6c21-4c16-82e8-9b50611f4dc1
Babiano, Reyes
b7ffd91c-bacd-4372-ab99-fc30ac2450ae
Cintas, Pedro
29979233-8382-47a8-bde7-1faf4869308c
Light, Mark
cf57314e-6856-491b-a8d2-2dffc452e161

Lavado, Nieves, García de la Concepción, Juan, Babiano, Reyes, Cintas, Pedro and Light, Mark (2019) Interactions of amino acids and aminoxazole derivatives: Cocrystal formation and prebiotic implications enabled by computational analysis. Origins of Life and Evolution of Biospheres, 1-23. (doi:10.1007/s11084-019-09582-9).

Record type: Article

Abstract

In line with the postulated intermediacy of aminoxazoles derived from small sugars toward the direct assembly of nucleoside precursors, we show here a potential prebiotic scenario where aminoxazolines might have also played further roles as complexing and/or sequestering agents of other primeval blocks, namely amino acids. To this end, a bis-aminoxazoline derivative, generated from dihydroxyacetone and cyanamide, gives rise to stable co-crystal forms with dicarboxylic amino acids (Asp and Glu), while ionic interactions owing to proton transfer are inferred from spectroscopic data in aqueous solution. The structure of a 1:2 aminoxazoline: aspartic acid complex, discussed in detail, was elucidated by X-ray diffractometry. Optimized geometries of such ionic structures with bulk aqueous solvation were assessed by DFT calculations, which disclose preferential arrangements that validate the experimental data. Peripherally, we were able to detect in a few cases amino acid dimerization (i.e. dipeptide formation) after prolonged incubation with the bis-aminoxazole derivative. A mechanistic simulation aided by computation provides some predictive conclusions for future explorations and catalytic design.

Text
REV-ORIG-D-19-00018R1 (002) - Accepted Manuscript
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Accepted/In Press date: 1 July 2019
e-pub ahead of print date: 20 July 2019
Keywords: Prebiotic chemistry, Amino acids, Aminoxazole chemistry, Reaction mechanism, Dipeptide

Identifiers

Local EPrints ID: 433555
URI: http://eprints.soton.ac.uk/id/eprint/433555
ISSN: 0169-6149
PURE UUID: 4ca960e6-0c10-46da-bf2e-9735bf9a873c
ORCID for Mark Light: ORCID iD orcid.org/0000-0002-0585-0843

Catalogue record

Date deposited: 27 Aug 2019 16:30
Last modified: 22 Nov 2021 07:37

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Contributors

Author: Nieves Lavado
Author: Juan García de la Concepción
Author: Reyes Babiano
Author: Pedro Cintas
Author: Mark Light ORCID iD

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