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

67 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.

Publisher Copyright:
© 2020 American Chemical Society.

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title = "Sequencing of Sequence-Defined Oligourethanes via Controlled Self-Immolation",

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.",

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

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. Publisher Copyright: {\textcopyright} 2020 American Chemical Society.",

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AU - Escamilla, P. Rogelio

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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.

N1 - 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. Publisher Copyright: © 2020 American Chemical Society.

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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