From Sequence‐Defined Macromolecules to Macromolecular Pin Codes

Abstract

Dynamic sequence‐defined oligomers carrying a chemically written pin code are obtained through a strategy combining multicomponent reactions with the thermoreversible addition of 1,2,4‐triazoline‐3,5‐diones (TADs) to indole substrates. The precision oligomers are specifically designed to be encrypted upon heating as a result of the random reshuffling of the TAD‐indole covalent bonds within the backbone, thereby resulting in the scrambling of the encoded information. The encrypted pin code can eventually be decrypted following a second heating step that enables the macromolecular pin code to be deciphered using 1D electrospray ionization‐mass spectrometry (ESI‐MS). The herein introduced concept of encryption/decryption represents a key advancement compared with current strategies that typically use uncontrolled degradation to erase and tandem mass spectrometry (MS/MS) to analyze, decipher, and read‐out chemically encrypted information. Additionally, the synthesized macromolecules are coated onto a high‐value polymer material, which demonstrates their potential application as coded product tags for anti‐counterfeiting purposes.

Synthesis and Encapsulation of Uniform Star‐Shaped Block‐Macromolecules

“…Sequence‐defined macromolecules can help to understand structure‐property or structure‐activity relationships, yet their synthesis mainly focused on linear architectures so far, which are, for instance, applied in data storage or the establishment of structure–property relationships. [ 22,25–32 ] However, multidirectional approaches, as well as more sophisticated structures like monodisperse star‐shaped macromolecules, have not been reported yet, probably due to the complexity of their synthesis. Closely related are dendrimers, which also come with a very narrow dispersity, but are often not completely uniform.…”

Desorption Electrospray Ionization (DESI) of Digital Polymers: Direct Tandem Mass Spectrometry Decoding and Imaging from Materials Surfaces

“…used molecular pin codes to label bank notes that had to be suspended for 5 h in ethanol to extract the encrypted tags, prior revealing them via heating in the presence of a trapping agent before ESI‐MS. [ 48 ]…”

Selective Bond Cleavage in Informational Poly(Alkoxyamine Phosphodiester)s

“…[3][4] Just like biological polymers, these macromolecules store information in a defined comonomer sequence. [5][6][7] Hence, this new field of research opens up unprecedented applications of synthetic polymers in areas such as data storage, [8][9][10][11][12][13] cryptography, [14][15] traceability, plastic recycling, [16] anti-counterfeiting technologies, [17][18] and synthetic Life. [19] Overall, the synthesis of information-containing macromolecules is a topic that is increasingly studied and welldocumented.…”