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Updated: Dec 20, 2025
09:34
Synthesis of Information-bearing Peptoids and their Sequence-directed Dynamic Covalent Self-assembly
Published on: February 6, 2020
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Selective Bond Cleavage in Informational Poly(Alkoxyamine Phosphodiester)s
Gianni Cavallo1, Jean-Louis Clément2, Didier Gigmes2
1Université de Strasbourg, CNRS, Institut Charles Sadron UPR22, 23 rue du Loess, Strasbourg Cedex 2, 67034, France.
Macromolecular Rapid Communications
|May 26, 2020
Summary
Collision-induced dissociation (CID) of sequence-defined polymers reveals selective bond cleavage. This research enables the development of readable, erasable, and programmable informational polymers for advanced applications.
Area of Science:
- Polymer Chemistry
- Mass Spectrometry
- Organic Synthesis
Background:
- Sequence-defined polymers offer precise control over material properties.
- Alkoxyamine-containing polymers are crucial for controlled radical polymerization and functionalization.
- Understanding fragmentation pathways is key to polymer characterization and design.
Purpose of the Study:
- To investigate the collision-induced dissociation (CID) behavior of sequence-defined poly(alkoxyamine phosphodiester)s.
- To explore selective bond cleavage in polymers synthesized with different nitroxide building blocks (proxyl, SG1, TEMPO).
- To assess the potential for designing "readable, erasable, or programmable" informational polymers.
Main Methods:
- Electrospray ionization mass spectrometry (ESI-MS).
- Tandem mass spectrometry (MS/MS) with controlled collision energies.
- Synthesis of sequence-defined poly(alkoxyamine phosphodiester)s using proxyl-, SG1-, and TEMPO-derivatives.
Main Results:
- Polymers with TEMPO- and SG1-alkoxyamines showed preferential cleavage at SG1 sites, enhanced by lower collision energy.
- Polymers with proxyl- and SG1-alkoxyamines exhibited selective bond cleavage at all collision energies.
- Sequential cleavage of SG1 followed by proxyl alkoxyamines was achieved in MS/MS and pseudo-MS3 conditions.
Conclusions:
- Collision-induced dissociation provides a powerful tool for characterizing sequence-defined polymers.
- Selective fragmentation pathways can be controlled by judicious choice of nitroxide building blocks and collision energy.
- These findings pave the way for novel informational polymers with tunable properties.
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