Premium
Cleavable Binary Dyads: Simplifying Data Extraction and Increasing Storage Density in Digital Polymers
Author(s) -
Cavallo Gianni,
Poyer Salomé,
Amalian JeanArthur,
Dufour Florent,
Burel Alexandre,
Carapito Christine,
Charles Laurence,
Lutz JeanFrançois
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201803027
Subject(s) - monomer , polymer , phosphoramidite , macromolecule , chemistry , sequence (biology) , extraction (chemistry) , combinatorial chemistry , computer science , materials science , chromatography , oligonucleotide , organic chemistry , dna , biochemistry
Digital polymers are uniform macromolecules that store monomer‐based binary sequences. Molecularly stored information is usually extracted from the polymer by a tandem mass spectrometry (MS/MS) measurement, in which the coded chains are fragmented to reveal each bit (i.e. basic coded monomer unit) of the sequence. Here, we show that data‐extraction can be greatly simplified by favoring the formation of MS/MS fragments containing two bits instead of one. In order to do so, digital poly(alkoxyamine phosphodiester)s, containing binary dyads in each repeat unit, were prepared by an orthogonal solid‐phase approach involving successive phosphoramidite and radical‐radical coupling steps. Three different sets of monomers were considered to build these polymers. In all cases, four coded building blocks—two hydroxy‐nitroxides and two phosphoramidite monomers—were required to build the dyads. Among the three studied monomer sets, one combination allowed synthesis of uniform sequence‐coded polymers. The resulting polymers led to clear dyad‐containing fragments in MS/MS and could therefore be efficiently decoded. Additionally, an algorithm was created to detect specific dyad fragments, thus enabling automated sequencing.