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Selective Bond Cleavage in Informational Poly(Alkoxyamine Phosphodiester)s
Author(s) -
Cavallo Gianni,
Clément JeanLouis,
Gigmes Didier,
Charles Laurence,
Lutz JeanFrançois
Publication year - 2020
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.202000215
Subject(s) - phosphodiester bond , chemistry , fragmentation (computing) , polymer , collision induced dissociation , tandem mass spectrometry , mass spectrometry , dissociation (chemistry) , electrospray ionization , cleavage (geology) , polymer chemistry , materials science , organic chemistry , chromatography , computer science , biochemistry , rna , fracture (geology) , composite material , gene , operating system
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‐MS 3 conditions. These results open up interesting new avenues for the design of readable, erasable or programmable informational polymers.