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Updated: Dec 20, 2025

Synthesis of Information-bearing Peptoids and their Sequence-directed Dynamic Covalent Self-assembly
Published on: February 6, 2020
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.
Abstract:
The collision-induced dissociation (CID) of sequence-defined poly(alkoxyamine phosphodiester)s is studied by electrospray ionization mass spectrometry. These informational polymers are synthesized using three different nitroxide building blocks, namely proxyl-, SG1-, and TEMPO-derivatives. For a polymer containing TEMPO- and SG1-based main chain alkoxyamines, it is found that both types of alkoxyamines break in CID tandem mass spectrometry (MS/MS). However, SG1-sites are preferentially cleaved and this predominance can be increased by reducing collision energy, even though selective bond fragmentation is not observed. On the other hand, for a polymer containing proxyl- and SG1-alkoxyamines, selective bond cleavage is observed at all studied collision energies. The SG1-alkoxyamines can be first cleaved in MS/MS conditions and secondly the proxyl-alkoxyamines in pseudo-MS3 conditions. These results open up interesting new avenues for the design of readable, erasable or programmable informational polymers.
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