Cleavable Binary Dyads: Simplifying Data Extraction and Increasing Storage Density in Digital Polymers

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.

A New Class of Materials: Sequence‐Defined Macromolecules and Their Emerging Applications

“…[12,13] Compared to DNA, synthetic polymer chemistry offers a unique opportunity to significantly increase the storage density. [8,15,16] Of course, designing macromolecules with distinct and facile fragmentation, [17,18] a computer assisted data interpretation [19] as well as a possible erasing of the data, [20] are essential to achieve practical application possibilities in the future. In terms of repeating units in sequence-defined macromolecules, this translates to the storage of one bit per repeat unit if a binary system (i.e., two different repeat units in a sequence-defined macromolecule) is used.…”

Silber‐ und Bronze‐Medaillen des CNRS 2018

“…Lutz untersucht sequenzkontrollierte Polymere, zuletzt mit dem Ziel der Entwicklung nichtbiologischer Polymere für die Speicherung sequenzkodierter Information auf molekularer Ebene. Sein aktuellster Beitrag in der Angewandten Chemie dreht sich um Datenextraktion und Speicherdichte digitaler Polymere; Lutz ist der Herausgeber eines Buchs über sequenzkontrollierte Polymere und Mitglied des Beirats der Macromolecular ‐Zeitschriften.…”

“…Carapito entwickelt quantitative Ansätze in der Massenspektrometrie. Sie ist Koautorin einer Angewandte‐Chemie ‐Zuschrift über Datenextraktion und Speicherdichte digitaler Polymere …”

CNRS Silver and Bronze Medals 2018

“…Lutz is interested in sequence‐controlled polymers, with a recent focus on the design of abiotic information‐containing polymers that allow storage of sequence‐coded messages at the molecular level. His most recent contribution to Angewandte Chemie is a report on data extraction and storage density in digital polymers, and he has edited a book on sequence‐controlled polymers . Lutz is on the Executive Advisory Board of the Macromolecular journals.…”