American Chemical Society
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Deracemization of a Dynamic Combinatorial Library Induced by (−)-Cytidine and (−)-2-Thiocytidine

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journal contribution
posted on 2008-09-03, 00:00 authored by Mee-Kyung Chung, Christine M. Hebling, James W. Jorgenson, Kay Severin, Stephen J. Lee, Michel R. Gagné
A dynamic combinatorial library composed of racemic hydrazone-based dipeptides becomes deracemized on binding to the chiral analytes (−)-cytidine and (−)-2-thiocytidine through the amplification of two receptors, (SS)-dimer and (RRRR)-tetramer. The deracemization phenomenon was investigated by laser polarimetry, mass-tagged pseudo-enantiomers in conjunction with electrospray ionization mass spectrometry, HPLC/UV-MS, UPLC/UV-MS, rapid-resolution LC-MS, collision-induced dissociation MS/MS, and numerical simulations. These data were consistent with a phenomenon where (SS)-dimer and (RRRR)-tetramer selectively bind the chiral analyte in preference to their enantiomeric counterparts, which ultimately causes them to be amplified and the library to become deracemized.