Overcoming GNA/RNA base-pairing limitations using isonucleotides improves the pharmacodynamic activity of ESC+ GalNAc-siRNAs.


Journal

Nucleic acids research
ISSN: 1362-4962
Titre abrégé: Nucleic Acids Res
Pays: England
ID NLM: 0411011

Informations de publication

Date de publication:
08 11 2021
Historique:
accepted: 27 09 2021
revised: 19 09 2021
received: 30 03 2021
pubmed: 15 10 2021
medline: 24 12 2021
entrez: 14 10 2021
Statut: ppublish

Résumé

We recently reported that RNAi-mediated off-target effects are important drivers of the hepatotoxicity observed for a subset of GalNAc-siRNA conjugates in rodents, and that these findings could be mitigated by seed-pairing destabilization using a single GNA nucleotide placed within the seed region of the guide strand. Here, we report further investigation of the unique and poorly understood GNA/RNA cross-pairing behavior to better inform GNA-containing siRNA design. A reexamination of published GNA homoduplex crystal structures, along with a novel structure containing a single (S)-GNA-A residue in duplex RNA, indicated that GNA nucleotides universally adopt a rotated nucleobase orientation within all duplex contexts. Such an orientation strongly affects GNA-C and GNA-G but not GNA-A or GNA-T pairing in GNA/RNA heteroduplexes. Transposition of the hydrogen-bond donor/acceptor pairs using the novel (S)-GNA-isocytidine and -isoguanosine nucleotides could rescue productive base-pairing with the complementary G or C ribonucleotides, respectively. GalNAc-siRNAs containing these GNA isonucleotides showed an improved in vitro activity, a similar improvement in off-target profile, and maintained in vivo activity and guide strand liver levels more consistent with the parent siRNAs than those modified with isomeric GNA-C or -G, thereby expanding our toolbox for the design of siRNAs with minimized off-target activity.

Identifiants

pubmed: 34648028
pii: 6396890
doi: 10.1093/nar/gkab916
pmc: PMC8565336
doi:

Substances chimiques

Ethylamines 0
Glycols 0
Oligoribonucleotides 0
Organophosphorus Compounds 0
Prealbumin 0
RNA, Double-Stranded 0
RNA, Small Interfering 0
Ttr protein, mouse 0
phosphoramidite 0
Guanosine 12133JR80S
isoguanosine 1818-71-9
dimethylformamide-dimethylacetal 4637-24-5
isocytidine 489-59-8
Cytidine 5CSZ8459RP
N,N-diisopropylethylamine 5SIQ15721L
Dimethylformamide 8696NH0Y2X
Alcohol Oxidoreductases EC 1.1.-
glycollate oxidase EC 1.1.3.15
Adenosine K72T3FS567
Acetylgalactosamine KM15WK8O5T

Types de publication

Journal Article Research Support, Non-U.S. Gov't

Langues

eng

Sous-ensembles de citation

IM

Pagination

10851-10867

Informations de copyright

© The Author(s) 2021. Published by Oxford University Press on behalf of Nucleic Acids Research.

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Auteurs

Mark K Schlegel (MK)

Alnylam Pharmaceuticals, Inc., Cambridge, MA 02142, USA.

Shigeo Matsuda (S)

Alnylam Pharmaceuticals, Inc., Cambridge, MA 02142, USA.

Christopher R Brown (CR)

Alnylam Pharmaceuticals, Inc., Cambridge, MA 02142, USA.

Joel M Harp (JM)

Department of Biochemistry, School of Medicine, Vanderbilt University, Nashville, TN 37232, USA.

Joseph D Barry (JD)

Alnylam Pharmaceuticals, Inc., Cambridge, MA 02142, USA.

Daniel Berman (D)

Alnylam Pharmaceuticals, Inc., Cambridge, MA 02142, USA.

Adam Castoreno (A)

Alnylam Pharmaceuticals, Inc., Cambridge, MA 02142, USA.

Sally Schofield (S)

Alnylam Pharmaceuticals, Inc., Cambridge, MA 02142, USA.

John Szeto (J)

Alnylam Pharmaceuticals, Inc., Cambridge, MA 02142, USA.

Muthiah Manoharan (M)

Alnylam Pharmaceuticals, Inc., Cambridge, MA 02142, USA.

Klaus Charissé (K)

Alnylam Pharmaceuticals, Inc., Cambridge, MA 02142, USA.

Martin Egli (M)

Department of Biochemistry, School of Medicine, Vanderbilt University, Nashville, TN 37232, USA.

Martin A Maier (MA)

Alnylam Pharmaceuticals, Inc., Cambridge, MA 02142, USA.

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Classifications MeSH