Precise alkoxyamine-design enables automated tandem mass spectrometry sequencing of digital poly(phosphodiester)s.

Fiche publication


Date publication

septembre 2020

Journal

Angewandte Chemie (International ed. in English)

Auteurs

Membres identifiés du Cancéropôle Est :
Dr CARAPITO Christine


Tous les auteurs :
Launay K, Amalian JA, Laurent E, Oswald L, Al Ouahabi A, Burel A, Dufour F, Carapito C, Clément JL, Lutz JF, Charles L, Gigmes D

Résumé

Increasing data storage density is one of the major challenges of the information industry. To be widely applicable, writing and reading information have to be dense, convenient and fast. A major step towards reliable reading of information coded in the sequence of long poly(phosphodiester)s was previously achieved by introducing an alkoxyamine spacer between information sub-segments. However, MS/MS decoding had to be performed manually to safely identify useful fragments of low abundance compared to side-products induced by the amide-based alkoxyamine used. Here, alternative alkoxyamines were designed to prevent these side-reactions and enable automated MS/MS sequencing. Different styryl-TEMPO spacers were prepared to increase radical delocalization and stiffness of the structure. Their dissociation behavior was investigated by EPR and best MS/MS data were recorded for polymers with alkoxyamines containing in-chain benzyl ring, avoiding all side-reactions during synthesis or sequencing. As a result, automated decoding of these polymers can be achieved using the MS-DECODER software, which performs interpretation of fragmentation data recorded for each sub-segment prior to align the so-obtained digital sequences in their original order based on the mass tag defining the initial location of each sub-segment.

Mots clés

alkoxyamine synthesis, digital information, mass spectrometry, radical ions, sequence-defined synthetic polymers

Référence

Angew. Chem. Int. Ed. Engl.. 2020 Sep 22;: