Cleavable Binary Dyads: Simplifying Data Extraction and Increasing Storage Density in Digital Polymers. Issue 21 (27th April 2018)

• Record Type: Journal Article
• Authors: Cavallo, Gianni; Poyer, Salomé; Amalian, Jean‐Arthur; Dufour, Florent; Burel, Alexandre; Carapito, Christine; Charles, Laurence; Lutz, Jean‐François
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 21(2018)
• Page Start: 6266
• Page End: 6269
• Publication Date: 2018-04-27
• Subjects: digital polymers -- mass spectrometry -- sequence-controlled polymers -- sequencing -- solid-phase chemistry; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201803027
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: 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. Abstract : Molecularly stored information : Digital oligo(alkoxyamine phosphodiester)s containing two bits of information per repeat unit were synthesized by an orthogonal solid‐phase multistep strategy. This optimal molecular design increases the information density of the digital polymer and greatly facilitates its sequencing by tandem mass spectrometry.