Biology
Scientific paper
Oct 2009
adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2009asbio...9..697p&link_type=abstract
Astrobiology, Volume 9, Issue 8, pp. 697-701.
Biology
Scientific paper
Spinomeric chemistry is a domain of physical chemistry that explores the role of spin-isomery in chemical reactivity. In large magnetic fields (B), chemical structures with three adjacent nuclear spins (such as H217O, H233O,-NH2 and 13CH2) form complex spinomers. Known departure from a 1:1 ratio between various types of spinomers opens interesting research avenues in their potential role in asymmetric hydration processes. Recent time domain 1H nuclear magnetic resonance (TD-1HNMR) findings revealed the existence of small, yet consistent, H217O-controlled enantio-different proton exchange reactivity in sugars. The mechanisms behind this effect are unclear and may involve spinomer/enantiocenter (e.g. H217O/*C) interactions or spinomer/spinomer (e.g. H217O-NH2) interactions. We developed an experimental model that allows for the verification and study of such effects. We used TD-1HNMR at 0.589T to study and compare proton exchange enantio-differences in asparagine (Asn) and mandelic acid in response to titration with at constant pH. Unlike Asn, mandelic acid has no complex spinomer group (such as -NH2) in its chiral center. We report finding enantio-differences regarding ΔpK and 1/T2(0) correlated with H217/O, and linear changes in ΔM2 indicating differences in the affinity of enantiomers for H217O surface hydration. These results stress the importance of H217O-based spinomeric chemistry in chiral reactivity and open windows toward a novel interpretation of the origin of prebiotic chiral reactivity in the presence of moderately large B (such as on magnetic mineral surfaces or on satellites of gaseous giants), as well as toward abiotic isotopic fractionation of H217O in the presence of chiral organic molecules.
Cimpoiaşu Vily Marius
Popa Radu
Scorei Romulus Ion
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