Thymine quintets and their higher order assemblies studied by electrospray ionization mass spectrometry and theoretical calculation
Citations Over TimeTop 16% of 2011 papers
Abstract
We previously reported that thymine molecules can specifically form a pentameric magic number cluster named as thymine quintet in the presence of K(+) , Rb(+) and Cs(+) . Actually, thymine decamer and doubly charged thymine 15-mer metaclusters can be observed along with thymine quintet in the ESI mass spectra of thymine with the addition of K(+) , Rb(+) and Cs(+) . The product ion spectra of these metaclusters, especially the 15-mer with hetero central ions, indicate that they are higher order assemblies of thymine quintets. The collision-induced dissociation experiments show that the gas-phase stabilities of these metaclusters depend on the size of the central ions, following the order Cs(+) > Rb(+) > K(+) , while K(+) leads to the highest dissociation energy of a thymine quintet. The optimized structures of thymine quintet and decamer were provided by density functional theory calculations, which showed that thymine quintet is bowl-shaped and its tilting angle increases with the size of the central ion. Furthermore, the chirality of thymine quintet was defined for the first time and the resulting different diastereoisomers of thymine decamers were also revealed by the calculation study. Copyright © 2011 John Wiley & Sons, Ltd.
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