Monodisperse, sequence-defined macromolecules as a tool to evaluate the limits of ring-closing metathesis

Wetzel, Katharina S.; Meier, Michael A. R.

doi:10.1039/c9py00438f

Cited by 7 publications

(13 citation statements)

References 72 publications

(13 reference statements)

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“…Oligomer synthesis. Since it has been demonstrated before that long sequences with or without side chain variation can be achieved in high overall yields and multigram scale by applying monomer M1 9,35 , the next step towards dual sequence-definition was to investigate if the backbone can be varied by utilising M1-M9. Thus, first an oligomer with a sequence-defined backbone (B1-7) was synthesised by varying the monomer in each reaction cycle (see Supplementary Methods for detailed experimental procedures).…”

Section: Resultsmentioning

confidence: 99%

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

et al. 2020

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Sequence-defined macromolecules offer applications in the field of data storage. Challenges include synthesising precise and pure sequences, reading stored information and increasing data storage capacity. Herein, the synthesis of dual sequence-defined oligomers and their application for data storage is demonstrated. While applying the well-established Passerini three-component reaction, the degree of definition of the prepared monodisperse macromolecules is improved compared to previous reports by utilising nine specifically designed isocyanide monomers to introduce backbone definition. The monomers are combined with various aldehyde components to synthesise dual-sequence defined oligomers. Thus, the side chains and the backbones of these macromolecules can be varied independently, exhibiting increased molecular diversity and hence data storage capacity per repeat unit. In case of a dual sequence-defined pentamer, 33 bits are achieved in a single molecule. The oligomers are obtained in multigram scale and excellent purity. Sequential read-out by tandem ESI-MS/MS verifies the high data storage capacity of the prepared oligomers per repeat unit in comparison to other sequence defined macromolecules.

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Section: Resultsmentioning

confidence: 99%

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

et al. 2020

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“…Therefore, multicomponent reactions, such as the Passerini‐3‐component reaction (P‐3CR), or “click chemistry” like in the azide‐alkyne cycloaddition, are often considered for this task. [ 15–21 ] The P‐3CR, which was already used by our working group to synthesize diverse linear and cyclic macromolecules, [ 14,22 ] was herein combined with the azide‐alkyne cycloaddition for the synthesis of uniform star‐shaped block co‐macromolecules. [ 23,24 ]…”

Section: Methodsmentioning

confidence: 99%

“…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.…”

Section: Methodsmentioning

confidence: 99%

“…For this purpose, we adapted an iterative cycle, which was already used by our group to synthesize a monodisperse icosamer, [ 14 ] as well as precursors for monodisperse macrocycles up to 152 ring atoms. [ 22 ] Yet, the procedure consisting of a P‐3CR (starting with a tetracarboxylic acid as the core scaffold) and subsequent hydrogenation of a benzylic ester, did not transfer well from mono/bidirectional to the new tetradirectional approach towards star‐shaped macromolecules. The P‐3CR worked in reliable manner, but the deprotection process was accompanied by an unknown coupling reaction, leading to molecules of higher mass (typically 0.2–1% of this side‐reaction took place, as determined by size exclusion chromatography (SEC)), which could not be separated from the main product.…”

Section: Methodsmentioning

confidence: 99%

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Synthesis and Encapsulation of Uniform Star‐Shaped Block‐Macromolecules

Waibel

Moatsou

Meier

2020

Macromol. Rapid Commun.

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Linear uniform oligomers synthesized via a two‐step iterative cycle are postmodified with uniform octaethylene glycol monomethyl ether and finally coupled via azide‐alkyne cycloaddition to yield uniform star‐shaped block macromolecules with a mass ranging from 10 to 14 kDa. Each of the molecules is carefully characterized by NMR, electrospray ionization mass spectrometry (ESI‐MS), and size exclusion chromatography (SEC) to underline their purity as well as their uniformity. The obtained star‐shaped macromolecules are investigated in their ability to encapsulate dye molecules by carrying out qualitative solid–liquid phase transfer experiments.

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“…The Passerini three component reaction (P-3CR), which was first reported in 1921 by Mario Passerini 24 , is wellestablished in the field of sequence-defined synthesis. It is also a versatile tool for the design of different types of sequences and architectures in combination with other reactions 6,16,21,23,[25][26][27][28] . The nearly quantitative yields allowed for the synthesis of long sequences with a high molecular weight in a high purity.…”

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Reading mixtures of uniform sequence-defined macromolecules to increase data storage capacity

2020

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In recent years, the field of molecular data storage has emerged from a niche to a vibrant research topic. Herein, we describe a simultaneous and automated read-out of data stored in mixtures of sequence-defined oligomers. Therefore, twelve different sequence-defined tetramers and three hexamers with different mass markers and side chains are successfully synthesised via iterative Passerini three-component reactions and subsequent deprotection steps. By programming a straightforward python script for ESI-MS/MS analysis, it is possible to automatically sequence and thus read-out the information stored in these oligomers within one second. Most importantly, we demonstrate that the use of mass-markers as starting compounds eases MS/MS data interpretation and furthermore allows the unambiguous reading of sequences of mixtures of sequence-defined oligomers. Thus, high data storage capacity considering the field of synthetic macromolecules (up to 64.5 bit in our examples) can be obtained without the need of synthesizing long sequences, but by mixing and simultaneously analysing shorter sequence-defined oligomers.

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Monodisperse, sequence-defined macromolecules as a tool to evaluate the limits of ring-closing metathesis

Abstract: Sequence-defined macromolecules of uniform size unlock the door to many new applications in polymer chemistry, such as structure/property or structure/activity relationship investigations, which cannot be conducted accurately, if the investigated macromolecules exhibit dispersity.

Cited by 7 publications

References 72 publications

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

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

Synthesis and Encapsulation of Uniform Star‐Shaped Block‐Macromolecules

Reading mixtures of uniform sequence-defined macromolecules to increase data storage capacity

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