Sequencing of Sequence-Defined Oligourethanes via Controlled Self-Immolation.

Sequencing of Sequence-Defined Oligourethanes via Controlled Self-Immolation.
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DOI:
10.1021/jacs.9b12818
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发表时间:
2020-02-12
影响因子:
15
通讯作者:
Anslyn EV
Anslyn EV
中科院分区:
化学1区
文献类型:
--
作者:
Dahlhauser SD;Escamilla PR;VandeWalle AN;York JT;Rapagnani RM;Shei JS;Glass SA;Coronado JN;Moor SR;Saunders DP;Anslyn EV

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序列限定的聚合物显示出仿生、自组装、催化和信息存储的前景,其中一级结构产生复杂的化学过程。在这里,我们报告了离散低聚氨基甲酸乙酯的液相和高产固相合成及其自分解测序方法,从而在不使用MS/MS的情况下快速和稳健地表征这类低聚物和聚合物。测序的关键是末端醇以受控和迭代的方式“解压缩”低聚物的固有反应性,以2-恶唑烷酮的形式释放每个单体。通过LC/MS监测自焚反应,应用算法快速产生寡氨基甲酸酯的序列。这个过程不仅提供了结构复杂分子的特征,它还可以作为分子信息的阅读器。
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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