Oligonucleotide Sequence Mapping of Large Therapeutic mRNAs via Parallel Ribonuclease Digestions and LC-MS/MS

Anal Chem. 2019 Jul 2;91(13):8500-8506. doi: 10.1021/acs.analchem.9b01664. Epub 2019 Jun 10.

Abstract

Characterization of mRNA sequences is a critical aspect of mRNA drug development and regulatory filing. Herein, we developed a novel bottom-up oligonucleotide sequence mapping workflow combining multiple endonucleases that cleave mRNA at different frequencies. RNase T1, colicin E5, and mazF were applied in parallel to provide complementary sequence coverage for large mRNAs. Combined use of multiple endonucleases resulted in significantly improved sequence coverage: greater than 70% sequence coverage was achieved on mRNAs near 3000 nucleotides long. Oligonucleotide mapping simulations with large human RNA databases demonstrate that the proposed workflow can positively identify a single correct sequence from hundreds of similarly sized sequences. In addition, the workflow is sensitive and specific enough to detect minor sequence impurities such as single nucleotide polymorphisms (SNPs) with a sensitivity of less than 1%. LC-MS/MS-based oligonucleotide sequence mapping can serve as an orthogonal sequence characterization method to techniques such as Sanger sequencing or next-generation sequencing (NGS), providing high-throughput sequence identification and sensitive impurity detection.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Chromatography, Liquid / methods*
  • Colicins / metabolism
  • DNA-Binding Proteins / metabolism
  • Endoribonucleases / metabolism
  • Erythropoietin / genetics
  • Erythropoietin / metabolism*
  • Escherichia coli Proteins / metabolism
  • High-Throughput Nucleotide Sequencing
  • Humans
  • Oligonucleotides / analysis*
  • Polymorphism, Single Nucleotide*
  • RNA, Messenger / genetics
  • RNA, Messenger / metabolism*
  • Ribonuclease T1 / metabolism
  • Sequence Analysis, RNA
  • Software
  • Tandem Mass Spectrometry / methods*
  • alpha Catenin / genetics
  • alpha Catenin / metabolism*

Substances

  • Colicins
  • DNA-Binding Proteins
  • EPO protein, human
  • Escherichia coli Proteins
  • MazF protein, E coli
  • Oligonucleotides
  • RNA, Messenger
  • alpha Catenin
  • Erythropoietin
  • Endoribonucleases
  • Ribonuclease T1