Sequence-Encoded Macromolecules with Increased Data Storage Capacity through a Thiol-Epoxy Reaction

Abstract

Sequence-encoded oligo(thioether urethane)s with two different coding monomers per backbone unit were prepared via a solid phase, two-step iterative protocol based on thiolactone chemistry. The first step of the synthetic cycle consists of the thiolactone ring opening with a primary amine, whereby the in situ released thiol is immediately reacted with an epoxide. In the second step, the thiolactone group is reinstalled to initiate the next cycle. This strategy allows to introduce two different coding monomers per synthetic cycle, rendering the resulting macromolecules especially attractive in the area of (macro)molecular data storage because of their increased data storage capacity. Subsequently, the efficiency of the herein reported synthesis route and the applicability of the dual-encoded sequence-defined macromolecules as a potential data storage platform have been demonstrated by unraveling the exact monomer order using tandem mass spectrometry techniques.

Rewritable Macromolecular Data Storage with Automated Read‐out

“…We have recently described the synthesis of oligo(thioether urethane)s, a promising class of dual sequence‐encoded macromolecules based on thiolactone chemistry [23] . These are obtained via aminolysis of the thiolactone, which introduces the first coding monomer, while the subsequent thiol‐epoxy reaction installs the second coding monomer, followed by a chain extension reaction (see Figure 1a).…”

“…Given the successful macromolecular encoding of the exemplary sentence, we aimed to read‐out the data before attempting the rewriting process. In our previous work, we relied on MALDI‐TOF/TOF as the method of choice for the fragmentation and subsequent determination of the monomer order of sequence‐defined macromolecules [23] . Moreover, an algorithm that is capable of translating a set of MS 2 spectra into the original data has also been developed [13] .…”

“…Even though Oligoreader is able to identify information‐containing macromolecules in an MS 1 spectrum and to deliver the corresponding building blocks, it is not possible to actually decode the information without MS 2 analysis. In previous work, we observed predominant fragmentation of the urethane bonds into an amine and an olefin, which were the result of a decarboxylation process [13, 23] . However, as we now relied on ESI‐MS/MS instead of MALDI‐TOF/TOF, we manually injected sequence WE5 and analyzed the obtained MS 2 spectrum.…”

Sequencing of Uniform Multifunctional Oligoesters via Random Chain Cleavages

“…On the other hand, the structure determination of monodisperse synthetic macromolecules has only more recently attracted widespread attention, mainly as a result of the advancements made within the area of sequence‐defined polymers [8] . These macromolecules are, amongst other applications, currently being investigated as a synthetic data storage platform, where digital information can be stored or encoded using the monomers’ order [9–18] . Sequencing information‐containing macromolecules is generally achieved by using MS/MS techniques, and different research groups have developed algorithms to facilitate the otherwise time‐consuming read‐out process [19–22] …”

Fabrication and Decryption of a Microarray of Digital Dithiosuccinimide Oligomers

“…[ 4–18 ] Inspired by this, chemists demonstrated sequence‐defined synthetic polymer can be used as an alternative data recorder, termed as digital polymer by Lutz et al [ 19–21 ] By employing two different monomers regarded as binary codes “0” and “1,” binary digital message can be encoded in the polymer chain through iterative synthetic strategies [ 22–35 ] and retrieved by tandem mass spectrometry (MS/MS) [ 36–46 ] as well as nanopore‐sequencing technique. [ 47,48 ] Compared to DNA, digital polymer displays higher chemical stability, better compatibility, and broader structural designability, [ 24,34,49,50 ] which improve the storage capacity [ 28,29,51–56 ] and facilitate decoding process [ 34,43,57–61 ] as well as applications. [ 44,53,62–66 ] While most of the efforts have been spent on novel structure and application design of digital polymers, few attentions were paid to implement the basic function of digital polymers, that is, designing a practical storing device or carrier of digital polymers for arbitrary writing and reading information in a reliable manner.…”