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Functionalization of acyclic xenonucleic acid with modified nucleobases

Polymer Journal volume 55, pages 743–752 (2023)Cite this article

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Abstract

Xenonucleic acids (XNAs), which are composed of artificial scaffolds and natural nucleobases, have unique hybridization properties that depend on the scaffold structure. Here, we functionalized the acyclic XNA serinol nucleic acid (SNA) with nonnatural nucleobases. A linear SNA probe functionalized with 5-perylenylethynyl uracil residues showed weak greenish-yellow excimer emission in the absence of target RNA and bright cyan-green monomer emission in the presence of target RNA. Probe hybridization was rapid and enabled the quantitative measurement of RNA with discrimination of single-base mismatches. We also designed a photoresponsive SNA with two 8-pyrenylvinyl adenine (PVA) residues. Irradiation with blue (455 nm) light caused [2 + 2] photocycloaddition between intrastrand PVAs, resulting in the dissociation of the SNA/RNA duplex, whereas irradiation with ultraviolet (340 nm) light induced cycloreversion of the PVA photodimer and SNA/RNA duplex reformation. Using a combination of 8-naphthylvinyl adenine (NVA) and PVA and irradiation with 465 nm, 405 nm, 340 nm, and 300 nm light, orthogonal control of the formation of SNA(NVA-NVA)/RNA and SNA(PVA-NVA)/RNA duplexes was demonstrated. Thus, nucleobase modifications further expand the utility of acyclic XNA in bionanotechnology.

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Acknowledgements

This work was supported by a Grant-in-Aid for Transformative Research Areas “Molecular Cybernetics” JP20H05970 (KM), 20H05968 (KM), JSPS KAKENHI grants JP20K15399 (KM), JP22J01195 (YY), JP22K14792 (YY), and JP21H05025 (HA). AMED under Grant Number 22am0401007 (HA) is also acknowledged.

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  1. Department of Biomolecular Engineering, Graduate School of Engineering, Nagoya University, Nagoya, Japan

    Keiji Murayama & Hiroyuki Asanuma

  2. Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai, Japan

    Yuuhei Yamano

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  1. Keiji Murayama
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Murayama, K., Yamano, Y. & Asanuma, H. Functionalization of acyclic xenonucleic acid with modified nucleobases. Polym J 55, 743–752 (2023). https://doi.org/10.1038/s41428-023-00776-7

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