Sequencing of Sequence-Defined Oligourethanes via Controlled Self-Immolation

Samuel D. Dahlhauser; P. Rogelio Escamilla; Abigail N. Vandewalle; Jordan T. York; Rachel M. Rapagnani; Jasper S. Shei; Samuel A. Glass; Jaime N. Coronado; Sarah R. Moor; Douglas P. Saunders; Eric V. Anslyn

doi:10.1021/jacs.9b12818

Sequencing of Sequence-Defined Oligourethanes via Controlled Self-Immolation

Samuel D. Dahlhauser, P. Rogelio Escamilla, Abigail N. Vandewalle, Jordan T. York, Rachel M. Rapagnani, Jasper S. Shei, Samuel A. Glass, Jaime N. Coronado, Sarah R. Moor, Douglas P. Saunders, Eric V. Anslyn

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

47 Scopus citations

Abstract

Sequence-defined polymers show promise for biomimetics, self-assembly, catalysis, and information storage, wherein the primary structure begets complex chemical processes. Here we report the solution-phase and the high-yielding solid-phase syntheses of discrete oligourethanes and methods for their self-immolative sequencing, resulting in rapid and robust characterization of this class of oligomers and polymers, without the use of MS/MS. Crucial to the sequencing is the inherent reactivity of the terminal alcohol to "unzip" the oligomers, in a controlled and iterative fashion, releasing each monomer as a 2-oxazolidinone. By monitoring the self-immolation reaction via LC/MS, an applied algorithm rapidly produces the sequence of the oligourethane. Not only does this process provide characterization of structurally complex molecules, it works as a reader of molecular information.

Original language	English (US)
Pages (from-to)	2744-2749
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	142
Issue number	6
DOIs	https://doi.org/10.1021/jacs.9b12818
State	Published - Feb 12 2020

Bibliographical note

Funding Information:
We gratefully acknowledge financial support for this work from the Army Research Office (W911NF-17-1-0522), the Howard Hughes Medical Institute (GT10481), and the Welch Reagents Chair to E.V.A. (F-0045). We would like to acknowledge the UT Mass Spectrometry Facility for their instrumental help and the UT NMR facilities for Bruker AVANCE III 500: NIH Grant Number 1 S10 OD021508-01.

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© 2020 American Chemical Society.

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abstract = "Sequence-defined polymers show promise for biomimetics, self-assembly, catalysis, and information storage, wherein the primary structure begets complex chemical processes. Here we report the solution-phase and the high-yielding solid-phase syntheses of discrete oligourethanes and methods for their self-immolative sequencing, resulting in rapid and robust characterization of this class of oligomers and polymers, without the use of MS/MS. Crucial to the sequencing is the inherent reactivity of the terminal alcohol to {"}unzip{"} the oligomers, in a controlled and iterative fashion, releasing each monomer as a 2-oxazolidinone. By monitoring the self-immolation reaction via LC/MS, an applied algorithm rapidly produces the sequence of the oligourethane. Not only does this process provide characterization of structurally complex molecules, it works as a reader of molecular information.",

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AU - York, Jordan T.

AU - Rapagnani, Rachel M.

AU - Shei, Jasper S.

AU - Glass, Samuel A.

AU - Coronado, Jaime N.

AU - Moor, Sarah R.

AU - Saunders, Douglas P.

AU - Anslyn, Eric V.

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PY - 2020/2/12

Y1 - 2020/2/12

N2 - Sequence-defined polymers show promise for biomimetics, self-assembly, catalysis, and information storage, wherein the primary structure begets complex chemical processes. Here we report the solution-phase and the high-yielding solid-phase syntheses of discrete oligourethanes and methods for their self-immolative sequencing, resulting in rapid and robust characterization of this class of oligomers and polymers, without the use of MS/MS. Crucial to the sequencing is the inherent reactivity of the terminal alcohol to "unzip" the oligomers, in a controlled and iterative fashion, releasing each monomer as a 2-oxazolidinone. By monitoring the self-immolation reaction via LC/MS, an applied algorithm rapidly produces the sequence of the oligourethane. Not only does this process provide characterization of structurally complex molecules, it works as a reader of molecular information.

AB - Sequence-defined polymers show promise for biomimetics, self-assembly, catalysis, and information storage, wherein the primary structure begets complex chemical processes. Here we report the solution-phase and the high-yielding solid-phase syntheses of discrete oligourethanes and methods for their self-immolative sequencing, resulting in rapid and robust characterization of this class of oligomers and polymers, without the use of MS/MS. Crucial to the sequencing is the inherent reactivity of the terminal alcohol to "unzip" the oligomers, in a controlled and iterative fashion, releasing each monomer as a 2-oxazolidinone. By monitoring the self-immolation reaction via LC/MS, an applied algorithm rapidly produces the sequence of the oligourethane. Not only does this process provide characterization of structurally complex molecules, it works as a reader of molecular information.

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Sequencing of Sequence-Defined Oligourethanes via Controlled Self-Immolation

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