Covalent Attachment and Detachment by Reactive DESI of Sequence‐Coded Polymer Taggants

Abstract

The use of sequence‐defined polymers is an interesting emerging solution for materials identification and traceability. Indeed, a very large amount of identification sequences can be created using a limited alphabet of coded monomers. However, in all reported studies, sequence‐defined taggants are usually included in a host material by noncovalent adsorption or entrapment, which may lead to leakage, aggregation, or degradation. To avoid these problems, sequence‐defined polymers are covalently attached in the present work to the mesh of model materials, namely acrylamide hydrogels. To do so, sequence‐coded polyurethanes containing a disulfide linker and a terminal methacrylamide moiety are synthesized by stepwise solid‐phase synthesis. These methacrylamide macromonomers are afterward copolymerized with acrylamide and bisacrylamide in order to achieve cross‐linked hydrogels containing covalently‐bound polyurethane taggants. It is shown herein that these taggants can be selectively detached from the hydrogel mesh by reactive desorption electrospray ionization. Using dithiothreitol the disulfide linker that links the taggant to the gel can be selectively cleaved. Ultimately, the released taggants can be decoded by tandem mass spectrometry.

Investigations for Material Tracing in Selective Laser Sintering: Part Ι: Methodical Selection of a Suitable Marking Agent

“…The use of the considered alternatives of modified polymers [ 37 , 55 , 59 , 60 , 62 , 88 ] and silicate-encapsulated DNA [ 53 , 58 ] is associated with high investment costs, especially due to the analytical technique ( Table 1 ). This evaluation criterion was not considered in the present work.…”

Digital synthetic polymers for information storage

“…7). 52 In a reactive mode of DESI, these covalently-bound taggants could be selectively cleaved from the gel network on demand by adding dithiothreitol (DTT) to reduce disulfide bonds and the released taggants can be decoded by MS/MS. Additionally, sequence-coded OUs can be transformed into the atom transfer radical polymerization (ATRP) macroinitiators using a three-step modification protocol, which can subsequently initiate the ATRP of styrene (Fig.…”

“…24 Remarkably, the barcode amplifications or other pre-analysis treatments are generally eliminated over the direct sequencereading of digital synthetic macromolecules. 24 Heretofore, a variety of digital synthetic macromolecules, such as poly(triazole amide)s, 32,33 polyphosphates, 24,[34][35][36][37][38][39][40][41] polyurethanes, [42][43][44][45][46][47][48][49][50][51][52] poly-(succinimide thioether)s, [53][54][55][56] poly(alkoxyamine amide)s, 57 have been created via multistep reactions, 23,58 copolyesters, 28 oligopeptides, 59 oligo(monothioacetal)s 60 and others, 61 opening up new avenues for molecular data storage.…”

Using precision polymer chemistry for plastics traceability and governance

“…Lutz and co-workers recently reported sequence-defined polymers, which are covalently bound to the material – in this case hydrogels – and retrievable by reactive desorption electrospray ionisation through a cleavable disulphide linker. 72 These binary encoded and material embedded labels were read-out by tandem mass spectrometry and since they are covalently bound, may significantly reduce the leakage risk over time.…”