Biopolymers such as DNA store information in their chains using controlled sequences of monomers. Here we describe a non-natural information-containing macromolecule that can store and retrieve digital information. Monodisperse sequence-encoded poly(alkoxyamine amide)s were synthesized using an iterative strategy employing two chemoselective steps: the reaction of a primary amine with an acid anhydride and the radical coupling of a carbon-centred radical with a nitroxide. A binary code was implemented in the polymer chains using three monomers: one nitroxide spacer and two interchangeable anhydrides defined as 0-bit and 1-bit. This methodology allows encryption of any desired sequence in the chains. Moreover, the formed sequences are easy to decode using tandem mass spectrometry. Indeed, these polymers follow predictable fragmentation pathways that can be easily deciphered. Moreover, poly(alkoxyamine amide)s are thermolabile. Thus, the digital information encrypted in the chains can be erased by heating the polymers in the solid state or in solution.
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http://dx.doi.org/10.1038/ncomms8237 | DOI Listing |
J Am Soc Mass Spectrom
June 2017
Precision Macromolecular Chemistry, Institut Charles Sadron, UPR22-CNRS, Strasbourg, France.
In order to improve their MS/MS sequencing, structure of sequence-controlled synthetic polymers can be optimized based on considerations regarding their fragmentation behavior in collision-induced dissociation conditions, as demonstrated here for two digitally encoded polymer families. In poly(triazole amide)s, the main dissociation route proceeded via cleavage of the amide bond in each monomer, hence allowing the chains to be safely sequenced. However, a competitive cleavage of an ether bond in a tri(ethylene glycol) spacer placed between each coding moiety complicated MS/MS spectra while not bringing new structural information.
View Article and Find Full Text PDFRapid Commun Mass Spectrom
January 2016
Precision Macromolecular Chemistry, Institut Charles Sadron, UPR22-CNRS, BP84047, 23 rue du Loess, 67034, Strasbourg Cedex 2, France.
Rationale: Digitally encoded oligomers composed of two distinct amide coding units spaced by a nitroxide moiety were recently decrypted using a tandem mass spectrometry (MS/MS) sequencing approach developed for protonated oligomers. Here, the MS/MS behavior of deprotonated oligomers was explored in the negative ion mode to provide both structural and mechanistic complementary information.
Methods: Binary-encoded oligo(alkoxyamine)amides, containing coding 0/1 amide units spaced by a TEMPO nitroxide moiety, were ionized in negative ion mode electrospray thanks to their α end-group containing a carboxylic acid function.
Chem Commun (Camb)
November 2015
Precision Macromolecular Chemistry Group, Institut Charles Sadron, 23 rue du Loess, BP84047, 67034 Strasbourg Cedex 2, France.
Binary-encoded poly(alkoxyamine amide)s were prepared by oligomer ligation. These polymers contain digital sequences based on two monomers defined as 0 and 1 bits. A library of oligomers containing all possible dyads 00, 01, 10 and 11 was prepared and used to construct long coded sequences.
View Article and Find Full Text PDFNat Commun
May 2015
Precision Macromolecular Chemistry, Institut Charles Sadron, UPR22-CNRS, BP84047, 23 rue du Loess, 67034 Strasbourg Cedex 2, France.
Biopolymers such as DNA store information in their chains using controlled sequences of monomers. Here we describe a non-natural information-containing macromolecule that can store and retrieve digital information. Monodisperse sequence-encoded poly(alkoxyamine amide)s were synthesized using an iterative strategy employing two chemoselective steps: the reaction of a primary amine with an acid anhydride and the radical coupling of a carbon-centred radical with a nitroxide.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!