Absolute configurations of spiroiminodihydantoin and allantoin stereoisomers: Comparison of computed and measured electronic circular dichroism spectra

Shuang Ding, Lei Jia, Alexander Durandin, Conor Crean, Alexander Kolbanovskiy, Vladimir Shafirovich, Suse Broyde, Nicholas E. Geacintov

Research output: Contribution to journalArticle

Abstract

The assignment of absolute configurations is of critical importance for understanding the biochemical processing of DNA lesions. The diastereomeric spiroiminodihydantoin (Sp) lesions are oxidation products of guanine and 8-oxo-7,8-dihydroguanine (8-oxoG), and the absolute configurations of the two diastereomers, Sp1 and Sp2, have been evaluated by experimental and computational optical rotatory dispersion (ORD) methods. In order to support our previous assignments by the ORD method, we calculated the electronic circular dichroism spectra (ECD) of the Sp stereoisomers. Comparison of the experimentally measured and computed ECD spectra indicates that Sp1 has (-)-S absolute configuration, while Sp2 has (+)-R absolute configuration. Thus, the S and R assignments, based on the ECD spectra of Sp1 and Sp2, are consistent with our previous assignments of absolute configurations. To further test the validity of this approach, we performed a proof-of-principle computation of the ECD and ORD of the R and S enantiomers of allantoin (similar in chemical composition to Sp) of known absolute configurations. The calculations provide the correct assignment of the absolute configurations of the allantoin enantiomers, indicating that the computational TDDFT approach is robust for identifying the absolute configurations of allantoins and probably the Sp stereoisomers, as has been shown previously for other organic molecules.

Original languageEnglish (US)
Pages (from-to)1189-1193
Number of pages5
JournalChemical research in toxicology
Volume22
Issue number6
DOIs
StatePublished - Jun 15 2009

ASJC Scopus subject areas

  • Toxicology

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