Cleavable Binary Dyads: Simplifying Data Extraction and Increasing Storage Density in Digital Polymers

Abstract

Digital polymers are uniform macromolecules that store monomer-based binary sequences.M olecularly stored information is usually extracted from the polymer by atandem mass spectrometry (MS/MS) measurement, in whichthe coded chains are fragmented to reveal each bit (i.e.b asic coded monomer unit) of the sequence.H ere,w es how that dataextraction can be greatly simplified by favoring the formation of MS/MS fragments containing two bits instead of one.I n order to do so,d igital poly(alkoxyamine phosphodiester)s, containing binary dyads in each repeat unit, were prepared by an orthogonal solid-phase approachi nvolving successive phosphoramidite and radical-radical coupling steps.T hree different sets of monomers were considered to build these polymers.I na ll cases,f our coded building blocks-two hydroxy-nitroxides and two phosphoramidite monomerswere required to build the dyads.A mong the three studied monomer sets,o ne combination allowed synthesis of uniform sequence-coded polymers.T he resulting polymers led to clear dyad-containing fragments in MS/MS and could therefore be efficiently decoded. Additionally,a na lgorithm was created to detect specific dyad fragments,t hus enabling automated sequencing.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Multifunctional sequence-defined macromolecules for chemical data storage

“…Various synthetic approaches have been developed to make sequences that can be easily read with well-known technologies such as tandem mass spectrometry 20 , 37 – 40 . Lutz and co-workers, for instance, stored digital information on sequence-defined oligourethanes 26 , 27 , oligo(triazole amide)s 28 , 29 , poly(phosphodiester)s 30 , 31 , oligo(alkoxyamine amide)s 32 , 33 and oligo(alkoxyamine phosphodiester)s 34 , 35 . In these sequences, digital information is encoded using two monomers, resulting in the binary representation commonly used by modern computer systems.…”

“…Thus, the use of sequence-defined structures with a large diversity of functionalities would allow for compact data storage on short macromolecular chains. The first examples of using multiple functionalities for data storage have recently been reported by the groups of Lutz 35 and Meier 44 .…”

Discrete and Stereospecific Oligomers Prepared by Sequential and Alternating Single Unit Monomer Insertion

“…vinyl monomers from petroleum industry) with defined monomer sequence and chirality as an alternative, due to their broad chemical diversity, relatively simple manipulation, and improved biostability. 12 Most importantly, such polymers have the potential to open new opportunities for the development of advanced materials for data storage, [13][14][15][16] catalysis [17][18] and drug delivery. [19][20][21] Various strategies have been proposed for regulating monomer sequence and chain length of synthetic polymers, including condensation chain polymerization, 22 alternating radical polymerization, [23][24][25][26][27][28][29] anionic polymerization, [30][31] ring-opening or cross metathesis polymerization, [32][33][34] atom transfer radical addition (ATRA), [24][25][35][36][37] iterative exponential growth, [38][39][40][41][42][43] single unit monomer insertion 12,[44][45][46][47][48][49][50] and various organic coupling, condensation or "click" addition reactions.…”

Dual sequence definition increases the data storage capacity of sequence-defined macromolecules

“…Besides the investigation of enhanced synthetic approaches, which further increase the degree of control, the potential applications of such defined structures gain increasing attention 16 . Particularly, the application in the field of data storage has been discussed in detail 2,31,32,[36][37][38][39][40] . The data storage capacity of DNA serves as prototype as it carries the genetic code 18,19 .…”