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Stacked and continuous helical self-assemblies of guanosine monophosphates detected by vibrational circular dichroism

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Abstract

The aim of this study was to characterize self-assembled structures of guanosine derivatives in aqueous solutions by vibrational circular dichroism (VCD) and electronic circular dichroism (ECD). Three guanosine derivatives were studied [5′-guanosine monophosphate (GMP), diphosphate (GDP), and triphosphate (GTP)] using a broad range of concentrations and various metal/guanosine ratios. VCD was used for the first time in this field and showed itself to be a powerful method for obtaining specific structural information in solution. It can also help to determine the impact that the cations have, when added to the solution, on the versatile structures of guanine derivatives in terms of their association and disassociation. Based on the markedly different intensities and signs of the VCD signals observed for different concentrations of guanosine derivatives, we propose various structures based on guanine quartets for high guanosine concentrations and high K+/guanosine ratios (i.e., columnar helical organization of the quartets, which are rearranged into a continuous helix). We performed a degenerate coupled oscillator (DCO) calculation to interpret the VCD spectra obtained and how they vary during the assembly of guanosine derivatives. The calculations correctly predicted the VCD spectra and enabled us to identify the structures of the metal cation/guanosine monophosphate aggregates. ECD in the ultraviolet region was used as a diagnostic tool to characterize the studied systems and as a contact point between the previously defined structures of the guanine derivative assemblies and the molecular systems studied here. These studies revealed that the VCD technique is a powerful new method for determining the structures of optically active guanosine motifs.

Proposed geometries of the guanosine adducts, the corresponding spectra calculated by the degenerate coupled oscillator method, and experimental vibrational circular dichroism spectra

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Acknowledgement

The work was supported by research grant P208/11/0105 from the Czech Science Foundation.

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Authors and Affiliations

  1. Department of Analytical Chemistry, Institute of Chemical Technology, Prague, Technická 5, 166 28, Prague, Czech Republic

    Iryna Goncharova & Jana Novotná

  2. Department of Physics and Measurements, Institute of Chemical Technology, Prague, Technická 5, 166 28, Prague, Czech Republic

    Marie Urbanová

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  1. Iryna Goncharova
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  2. Jana Novotná
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  3. Marie Urbanová
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Correspondence to Marie Urbanová.

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Goncharova, I., Novotná, J. & Urbanová, M. Stacked and continuous helical self-assemblies of guanosine monophosphates detected by vibrational circular dichroism. Anal Bioanal Chem 403, 2635–2644 (2012). https://doi.org/10.1007/s00216-012-6014-7

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  • DOI: https://doi.org/10.1007/s00216-012-6014-7

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