Fabrication and Decryption of a Microarray of Digital Dithiosuccinimide Oligomers

Abstract

Digital polymers with precisely arranged binary units provide an important option for information storage. This is especially true if the digital polymers are assembled in a device, as it would be of great benefit for data writing and reading in practice. Herein, inspired by the DNA microarray technique, the programmable information storing and reading on a mass spectrometry target plate is proposed. First, an array of 4‐bit sequence‐coded dithiosuccinimide oligomers is efficiently built through sequential thiol‐maleimide Michael couplings with good sequence readability by tandem mass spectrometry (MS/MS). Then, toward engineering microarrays for information storage, a programmed robotic arm is specifically designed for precisely loading sequence‐coded oligomers onto the target plate, and a decoding software is developed for efficient readout of the data from MS/MS sequencing. Notably, short sequence‐coded oligomer chains can be used to write long strings of information, and extra error‐correction codes are not required as usual due to the inherent concomitant fragmentation signals. Not only text but also bitimages can be automatically stored and decoded with excellent accuracy. This work provides a promising platform of digital polymers for programmable information storing and reading.

Reading Information Stored in Synthetic Macromolecules

“…In parallel, Zhang and coworkers developed another algorithm, Universal Tandem Mass Decoder, to ease the sequencing of binary-encoded tetramers based on a thiol−maleimide coupling. 22 In this instance, 325 MS/MS spectra could be accurately decoded in less than 14 s, demonstrating the effectiveness of the software.…”

“…Indeed, the calculation times are dependent on the number of possible permutations, which means that an enlarged molecular alphabet would rapidly increase the overall time required for MS-DECODER to decipher the tandem MS spectra. In parallel, Zhang and co-workers developed another algorithm, Universal Tandem Mass Decoder , to ease the sequencing of binary-encoded tetramers based on a thiol–maleimide coupling . In this instance, 325 MS/MS spectra could be accurately decoded in less than 14 s, demonstrating the effectiveness of the software.…”

“…The main advantage of using synthetic macromolecules rather than biomacromolecules is the fact that the former can be synthesized using a wide range of monomers. , As a result, they can be tailor-made upon desire, since the main limiting factor in their design is the inspiration and synthetic ability of the chemist. As a consequence, numerous groups have already demonstrated that a series of chemically diverse, sequence-defined macromolecules can be readily used to encode information at the molecular level. − Moreover, as a result of the increased thermal and hydrolytic stability provided by selected synthetic backbones, synthetic sequence-defined macromolecules are currently also being investigated within the area of anti-counterfeiting tags. − For this, small amounts of specifically encoded macromolecules are added to valuable goods as an extra layer of protection to avoid the forgery of the product.…”

Digital synthetic polymers for information storage

“…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

“…By far the most prominent method for reading-out the information encoded into the structure of sequence-defined polymers is via high resolution mass spectrometry (MS). In particular, tandem MS/MS techniques have been widely employed, 49,56,60,61,63,[65][66][67][68][69] though examples of single electrospray ionisation MS techniques as read-out methods also exist. 26,70 Tandem MS/MS enables the specific fragmentation of the sequence-defined structure, as determined by its molecular design.…”