@article{Jimmy Huang-2018-Instantaneous,
title = "Instantaneous Iodine-Assisted DNAzyme Cleavage of Phosphorothioate RNA",
author = "Huang, Po‐Jung Jimmy and
Moon, Woohyun J. and
Liu, Juewen",
journal = "Biochemistry, Volume 58, Issue 5",
volume = "58",
number = "5",
year = "2018",
publisher = "American Chemical Society (ACS)",
url = "https://gwf-uwaterloo.github.io/gwf-publications/G18-57001",
doi = "10.1021/acs.biochem.8b00900",
pages = "422--429",
abstract = "Metal ions play a critical role in the RNA-cleavage reaction by interacting with the scissile phosphate and stabilizing the highly negatively charged transition state. Many metal-dependent DNAzymes have been selected for RNA cleavage. Herein, we report that the Ce13d DNAzyme can use nonmetallic iodine (I2) to cleave a phosphorothioate (PS)-modified substrate. The cleavage yield exceeded 60{\%} for both the Rp and Sp stereoisomers in 10 s, while the yield without the enzyme strand was only ∼10{\%}. The Ce13d cleavage with I2 also required Na+, consistent with the property of Ce13d and confirming the similar role of I2 as a metal ion. Ce13d had the highest yield among eight tested DNAzymes, with the second highest DNAzyme showing only 20{\%} cleavage. The incomplete cleavage was due to competition from desulfurization and isomerization reactions. This DNAzyme was engineered for fluorescence-based I2 detection. With EDTA for masking metal ions, I2 was selectively detected down to 4.7 nM. Oxidation of I- with Fe3+ produced I2 in situ, allowing detection of Fe3+ down to 78 nM. By harnessing nonelectrostatic interactions, such as the I2/sulfur interaction observed here, more nonmetal species might be discovered to assist DNAzyme-based RNA cleavage.",
}
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<abstract>Metal ions play a critical role in the RNA-cleavage reaction by interacting with the scissile phosphate and stabilizing the highly negatively charged transition state. Many metal-dependent DNAzymes have been selected for RNA cleavage. Herein, we report that the Ce13d DNAzyme can use nonmetallic iodine (I2) to cleave a phosphorothioate (PS)-modified substrate. The cleavage yield exceeded 60% for both the Rp and Sp stereoisomers in 10 s, while the yield without the enzyme strand was only ∼10%. The Ce13d cleavage with I2 also required Na+, consistent with the property of Ce13d and confirming the similar role of I2 as a metal ion. Ce13d had the highest yield among eight tested DNAzymes, with the second highest DNAzyme showing only 20% cleavage. The incomplete cleavage was due to competition from desulfurization and isomerization reactions. This DNAzyme was engineered for fluorescence-based I2 detection. With EDTA for masking metal ions, I2 was selectively detected down to 4.7 nM. Oxidation of I- with Fe3+ produced I2 in situ, allowing detection of Fe3+ down to 78 nM. By harnessing nonelectrostatic interactions, such as the I2/sulfur interaction observed here, more nonmetal species might be discovered to assist DNAzyme-based RNA cleavage.</abstract>
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%0 Journal Article
%T Instantaneous Iodine-Assisted DNAzyme Cleavage of Phosphorothioate RNA
%A Huang, Po‐Jung Jimmy
%A Moon, Woohyun J.
%A Liu, Juewen
%J Biochemistry, Volume 58, Issue 5
%D 2018
%V 58
%N 5
%I American Chemical Society (ACS)
%F JimmyHuang-2018-Instantaneous
%X Metal ions play a critical role in the RNA-cleavage reaction by interacting with the scissile phosphate and stabilizing the highly negatively charged transition state. Many metal-dependent DNAzymes have been selected for RNA cleavage. Herein, we report that the Ce13d DNAzyme can use nonmetallic iodine (I2) to cleave a phosphorothioate (PS)-modified substrate. The cleavage yield exceeded 60% for both the Rp and Sp stereoisomers in 10 s, while the yield without the enzyme strand was only ∼10%. The Ce13d cleavage with I2 also required Na+, consistent with the property of Ce13d and confirming the similar role of I2 as a metal ion. Ce13d had the highest yield among eight tested DNAzymes, with the second highest DNAzyme showing only 20% cleavage. The incomplete cleavage was due to competition from desulfurization and isomerization reactions. This DNAzyme was engineered for fluorescence-based I2 detection. With EDTA for masking metal ions, I2 was selectively detected down to 4.7 nM. Oxidation of I- with Fe3+ produced I2 in situ, allowing detection of Fe3+ down to 78 nM. By harnessing nonelectrostatic interactions, such as the I2/sulfur interaction observed here, more nonmetal species might be discovered to assist DNAzyme-based RNA cleavage.
%R 10.1021/acs.biochem.8b00900
%U https://gwf-uwaterloo.github.io/gwf-publications/G18-57001
%U https://doi.org/10.1021/acs.biochem.8b00900
%P 422-429
Markdown (Informal)
[Instantaneous Iodine-Assisted DNAzyme Cleavage of Phosphorothioate RNA](https://gwf-uwaterloo.github.io/gwf-publications/G18-57001) (Huang et al., GWF 2018)
ACL
- Po‐Jung Jimmy Huang, Woohyun J. Moon, and Juewen Liu. 2018. Instantaneous Iodine-Assisted DNAzyme Cleavage of Phosphorothioate RNA. Biochemistry, Volume 58, Issue 5, 58(5):422–429.