Enantiodifferent Proton Exchange in Alanine and Asparagine in the Presence of H 2 17 O

Abstract

Using Time Domain (1)H Nuclear Magnetic Resonance with H (2) (17) O (H (2) (17) O-TD-(1)HNMR), we found [H (2) (17) O]- and pH-controlled chiral differences in proton exchange properties in alanine (Ala) and asparagine (Asn). To minimize and equalize chemical impurities, Asn enantiomers were purified by crystallization from racemic solution. At <0.1 M H (2) (17) O, a shift in isoelectric pH (pI) occurred, approximately 1.14 kJ mol(-1) L: -D: -Asn DeltaDeltaG (o)' in the 5.91-6.42 pH range. One potential source for this asymmetry is the enantio-different magnetic moments (L: mu upward arrow not equal D: mu downward arrow) produced by neutral ring currents in the chiral center, leading to enantio-different nuclear spin organization and charge distribution in the amino group. At >or=pI, dissimilar interactions may occur in the hydration of the amino group with H (2) (17) O (NH(2)/H (2) (17) O not equal NH(2)/H (2) (16) O; NH(3) (+)/H (2) (17) O not equal NH(2)/H (2) (17) O; L: -*C-NH(2)/H (2) (17) O not equal D: -*C-NH(2)/H (2) (17) O). As L: mu upward arrow not equal D: mu downward arrow, the L: -*C-amino and the D: -*C-amino groups are diastereo spin-isomers. The nuclear spin of (17)O may be parallel or antiparallel with the ortho-(1)H(1)H pair; hence two ortho-H (2) (17) O molecules exist, also diastereo spin-isomers. As the pK of H (2) (17) O is different from H (2) (16) O, dissimilarities between L: -*C- and D: -*C-amino groups are converted into proton exchange differences. During H (2) (17) O-TD-(1)HNMR, the H (2) (17) O molecule is a "probe" of the state of the amino group. Regarding prebiotic evolution: prebiotic chirality may not require stochastic symmetry breaking or preexisting chiral conditions; chemical chiral effects due to L: mu upward arrow not equal D: mu downward arrow are small and need chiral amplification to generate an enantiomeric excess significant for prebiotic evolution; and prebiotic symmetry breaking was homochiral because the effect of L: mu upward arrow and D: mu downward arrow on the amino group should be similar in all alpha amino acids.