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Introduction Oligonucleotide therapeutics have emerged in recent years as a powerful alternative to small molecule and protein therapeutics. Manufacturing and quality control of oligonucleotide therapeutics requires highly selective and sensitive LC/MS methods for impurity identification and quantification. Here we demonstrate the use of a novel chromatographic system, equipped with a modified surface technology across its entire fluidic path [1], for analysis of modified synthetic oligonucleotides and their impurities. Methods Separations were performed by ion-pairing RP chromatography on a 2.1 x 100 mm UHPLC column with a modified internal surface, packed with 1.7 µm C18 particles. UV chromatograms were acquired on a tunable UV detector at a wavelength of 260 nm. High resolution (> 10,000) ESI-MS spectra were acquired in negative ion mode on a TOF MS instrument using an acquisition time of 0.5 sec. The accuracy of each intact mass measurement was calculated by comparing the experimentally obtained deconvoluted mass against the theoretical average masses of each oligo. Preliminary data The first type of modified oligonucleotide characterized was a 21-mer, bearing 19 modified nucleosides, while the second type was a 100-mer single guide (sg) RNA oligo. Chelating interactions occurring between oligonucleotides and metal surfaces can be mitigated by employing a UHPLC system with a fluidic path containing a hybrid organic/inorganic barrier layer [1] which minimizes the contact of analytes (oligonucleotides) with the metal surfaces present in the fluidic path or the UHPLC column. The data presented here demonstrates that a combination of the bio-inert UHPLC system and column is critical for obtaining accurate results in measuring low-level oligonucleotide impurities (down to 0.2% relative abundance levels) using UV detection at 260 nm. In addition, the same LC-MS platform provides intact mass confirmation of oligonucleotides and their impurities with mass accuracies under 15 ppm. References: 1. Anal Chem, 2021, 93, p5773.

Contact Information

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Ann Gray

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Team Members

Ann Gray profile image

Ann Gray

Waters Corporation

Presenter
Ann Gray
Waters Corporation
Email: ann_gray@waters.com
Christopher Knowles profile image

Christopher Knowles

Waters Corporation

Co-Author
Christopher Knowles
Waters Corporation
Email: christopher_knowles@waters.com
Emma Harry profile image

Emma Harry

Waters Corporation

Co-Author
Emma Harry
Waters Corporation
Email: emma_harry@waters.com
Jonathan Fox profile image

Jonathan Fox

Waters Corporation

Co-Author
Jonathan Fox
Waters Corporation
Email: jonathan_fox@waters.com
Joseph Fredette profile image

Joseph Fredette

Waters Corporation

Co-Author
Joseph Fredette
Waters Corporation
Email: joseph_fredette@waters.com
Weibin Chen profile image

Weibin Chen

Waters Corporation

Co-Author
Weibin Chen
Waters Corporation
Email: weibin_chen@waters.com
Ying-Qing Yu profile image

Ying-Qing Yu

Waters Corporation

Co-Author
Ying-Qing Yu
Waters Corporation
Email: ying_qing_yu@waters.com
Catalin Doneanu profile image

Catalin Doneanu

Waters Corporation

Principal Chemist
Catalin Doneanu
Waters Corporation
34 Maple Street
Milford, MA 01757
United States
Email: catalin_doneanu@waters.com