Direct comparison of solution and solid phase synthesis of sequence-defined macromolecules

Holloway, Joshua O.; Wetzel, Katharina S.; Martens, Steven; Prez, Filip Du; Meier, Michael

doi:10.1039/c9py00558g

Cited by 37 publications

(34 citation statements)

References 61 publications

(101 reference statements)

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“…Such macromolecules with a distinct order of the monomer units and a defined length are termed "uniform" molecules according to IUPAC 1 . Many routes towards sequence-defined structures have been developed over the last years, aiming for an increasing degree of control and precision [2][3][4][5][6][7][8][9][10][11][12][13][14][15] . The sequence-defined structures represent a new class of molecules in the polymer area, combining the features of classic polymers that are consisting of many repeating units, thus leading to their characteristic properties, with the ones of organic molecules, being uniform in size as well as constitution and topology.…”

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“…Stepwise iterative approaches are a common route towards sequence-defined structures, since this step-by-step growth offers full control over the respective monomer units 4,5,9,13,[20][21][22][23][24][25][26][27][28][29][30][31] . Multicomponent reactions are a well-established tool for achieving sequence-definition, as their modular character as well as their scalability and nearly quantitative yields, often without formation of any side products, are important features for the efficient synthesis of long sequences 3,22,23,32,33 . In particular, the Passerini three-component reaction (P-3CR) between a carboxylic acid, an aldehyde and an isocyanide, which was first reported in 1921 by the Italian chemist Mario Passerini 34 , has been proven to be a powerful tool in the synthesis of sequence-defined macromolecules of both high molecular weight and purity.…”

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

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“…For this, a recently established iterative synthesis protocol that combines the reactivity of TADs with the P‐3CR multicomponent reaction was modified in order to implement the required thermoreversible linkages within the sequence. [ 37 ] Indeed, changing one of the reagents from a conjugated diene to an indole‐containing moiety would alter the nature of the formed covalent TAD linkage within the sequence from an irreversible to a thermally reversible one. [ 34 ] Thus, the TAD carboxylic acid (TAD‐COOH) building blocks ( L1a ‐ b , Figure ) were combined with four different indole‐aldehyde analogues ( L2a‐d ) to act as dynamic TAD reaction partners.…”

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From Sequence‐Defined Macromolecules to Macromolecular Pin Codes

et al. 2020

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Dynamic sequence‐defined oligomers carrying a chemically written pin code are obtained through a strategy combining multicomponent reactions with the thermoreversible addition of 1,2,4‐triazoline‐3,5‐diones (TADs) to indole substrates. The precision oligomers are specifically designed to be encrypted upon heating as a result of the random reshuffling of the TAD‐indole covalent bonds within the backbone, thereby resulting in the scrambling of the encoded information. The encrypted pin code can eventually be decrypted following a second heating step that enables the macromolecular pin code to be deciphered using 1D electrospray ionization‐mass spectrometry (ESI‐MS). The herein introduced concept of encryption/decryption represents a key advancement compared with current strategies that typically use uncontrolled degradation to erase and tandem mass spectrometry (MS/MS) to analyze, decipher, and read‐out chemically encrypted information. Additionally, the synthesized macromolecules are coated onto a high‐value polymer material, which demonstrates their potential application as coded product tags for anti‐counterfeiting purposes.

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“…Based on significant progress in precision polymer chemistry, synthetic control over chain lengths [43][44][45][46][47] and monomer sequences [48][49][50][51] has been largely achieved and enabled the synthesis of uniform sequence defined polymers. [52][53][54] Compared to the levels of protein structures -the natural inspiration of SCNPs -the current state-of-the-art allows controlling the primary structure, i.e. monomer sequence, of the linear polymer precursor reasonably well.…”

Section: Secondary Structure Inspired Order Of Subdomainsmentioning

confidence: 99%

Macromolecular Superstructures: A Future Beyond Single Chain Nanoparticles

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Tuten

Barner‐Kowollik

2020

Israel Journal of Chemistry

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Over the last 100 years polymer chemistry has flourished in all areas and enabled control over synthetic polymer architectures – including chain lengths, dispersity and monomer sequences. Compared to the architectures of biomacromolecules, these scientific achievements mainly took place on the level of primary structures. The plethora of functions carried out by proteins in nature, however, does not only result from their primary structure, but from its folding into perfectly defined 3D structures. Striving towards a similar architectural control and function in synthetic polymers, the field of single chain nanoparticles (SCNPs) emerged. In this review, we analyze the state of the art and identify what is currently standing between polymer chemistry and perfectly controlled synthetic macromolecular architectures. Based on the current challenges in the field of SCNPs, we discuss potential avenues to break today's barriers and explore future applications reaching beyond the current‐state‐of‐the‐art.

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Direct comparison of solution and solid phase synthesis of sequence-defined macromolecules

Abstract: Sequence-defined macromolecules of high molecular weight are synthesised by the combination of click chemistry with multicomponent reactions. The synthesis is performed on solid phase as well as in solution to directly compare the two approaches.

Cited by 37 publications

References 61 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

From Sequence‐Defined Macromolecules to Macromolecular Pin Codes

Macromolecular Superstructures: A Future Beyond Single Chain Nanoparticles

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