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Rooting Prebiotic Chirality in Spinomeric Chemistry?

Authors: Radu, Popa; Vily Marius, Cimpoiaşu; Romulus Ion, Scorei;

Rooting Prebiotic Chirality in Spinomeric Chemistry?

Abstract

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 H(2)(17)O, H(2)(33)S,-NH(2), and and -(13)CH(2)-) 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 (1)H nuclear magnetic resonance (TD-(1)HNMR) findings revealed the existence of small, yet consistent, H(2)(17)O-controlled enantio-different proton exchange reactivity in sugars. The mechanisms behind this effect are unclear and may involve spinomer/enantiocenter (e.g., H(2)(17)O/*C) interactions or spinomer/spinomer (e.g., H(2)(17)O/-NH(2)) interactions. We developed an experimental model that allows for the verification and study of such effects. We used TD-(1)HNMR at 0.589 T to study and compare proton exchange enantio-differences in asparagine (Asn) and mandelic acid in response to titration with H(2)(17)O at constant pH. Unlike Asn, mandelic acid has no complex spinomer group (such as -NH(2)) in its chiral center. We report finding enantio-differences regarding DeltapK and 1/T(2)(0) correlated with H(2)(17)O, and linear changes in DeltaM(2) indicating differences in the affinity of enantiomers for H(2)(17)O surface hydration. These results stress the importance of H(2)(17)O-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 H(2)(17)O in the presence of chiral organic molecules.

Related Organizations
Keywords

Magnetic Resonance Spectroscopy, Time Factors, Molecular Structure, Chemistry, Physical, Water, Hydrogen Bonding, Hydrogen-Ion Concentration, Oxygen, Kinetics, Isomerism, Mandelic Acids, Isoelectric Point, Asparagine, Protons

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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
5
Average
Average
Average
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