Covalent Attachment and Detachment by Reactive DESI of Sequence‐Coded Polymer Taggants. Issue 21 (14th July 2022)

• Record Type: Journal Article
• Authors: Youssef, Itab; Carvin‐Sergent, Isaure; Konishcheva, Evgeniia; Kebe, Seydina; Greff, Vincent; Karamessini, Denise; Matloubi, Maziar; Ouahabi, Abdelaziz Al; Moesslein, Jochen; Amalian, Jean‐Arthur; Poyer, Salomé; Charles, Laurence; Lutz, Jean‐François
• Is Part Of: Macromolecular rapid communications. Volume 43:Issue 21(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-07-14
• Subjects: anti‐counterfeiting technologies -- desorption electrospray ionization -- materials traceability -- secure materials -- sequence‐controlled polymers; Macromolecules -- Periodicals; Polymers -- Periodicals; Chemistry -- Periodicals; 547.705
• DOI: 10.1002/marc.202200412
• Languages: English
• ISSNs: 1022-1336

Abstract

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. Abstract : Polymer taggants, containing a sequence‐coded polyurethane segment connected to a cleavable disulfide linker and a polymerizable methacrylamide terminus, are synthesized by stepwise iterative chemistry. They are covalently included in acrylamide hydrogels by radical copolymerization. Furthermore, they can be selectively cleaved from the gel mesh by reactive desorption electrospray ionization using the reducing agent dithiothreitol and decoded by tandem mass spectrometry.