Efficient molecular encoding in multifunctional self-immolative urethanes

Abstract

SUMMARY Molecular encoding in sequence-defined polymers shows promise as a new paradigm for data storage. Here, we report what is, to our knowledge, the first use of self-immolative oligourethanes for storing and reading encoded information. As a proof of principle, we describe how a text passage from Jane Austen’s Mansfield Park was encoded in sequence-defined oligourethanes and reconstructed via self-immolative sequencing. We develop Mol.E-coder, a software tool that uses a Huffman encoding scheme to convert the character table to hexadecimal. The oligourethanes are then generated by a high-throughput parallel synthesis. Sequencing of the oligourethanes by self-immolation is done concurrently in a parallel fashion, and the liquid chromatography-mass spectrometry (LC-MS) information decoded by our Mol.E-decoder software. The passage is capable of being reproduced wholly intact by a third-party, without any purifications or the use of tandem MS (MS/MS), despite multiple rounds of compression, encoding, and synthesis.

Recent advances in self-immolative linkers and their applications in polymeric reporting systems

“…336 Excitingly, the potential in information storage has been addressed in a recent paper. 337 In addition to information storage, this system also has potential in areas such catalysis and self-assembly.…”

“…342 These modified PBEs featured a phenolic end group and thus were depoly-Scheme 91 Oligocarbamates information storage systems such as 365 reported by Anslyn and co-workers. 335,337 Scheme 92 Disassembly pathway of a self-immolative poly(benzyl ether)-based polymer 366 with different triggers.…”

Molecular data storage with zero synthetic effort and simple read-out

“…Kéki focused on an alcohol-isocyanate click approach for the synthesis of encoded polyethylene glycol 41 . In 2021, Yao et al published the storage of data in peptide sequences 42 , and Anslyn and coworkers in self-immolative sequence defined urethanes 43 . These approaches are all based on using two monomer units, resulting in a binary code along the sequence.…”

Sequencing of Uniform Multifunctional Oligoesters via Random Chain Cleavages

“…[23] Another strategy for generating a series of truncated structures consists of the depolymerization of synthetic macromolecules, an approach that was recently adopted by Van Anslyn and co-workers. [24,25] They reported the elegant sequencing of sequence-defined oligourethanes via a controlled self-immolation process. In this case, the terminal hydroxyl moiety was capable of participating in an intramolecular cyclization process, leading to the partial depolymerization of the oligourethanes.…”

“…By calculating the mass difference between the different peaks in the LC-chromatogram, the monomer order of M4 could be readily determined. Even though one would expect such an LC-trace in the case of a controlled depolymerization, as is the case for oligourethanes, [24,25] the installation of a long-wavelength chromophore conveniently delivered all truncated structures upon the introduction of random chain cleavages. In addition, the uncontrolled nature of the process enables the use of very short reaction times as the formation of all iterations occurs at a comparable rate.…”