Aix Marseille Université, CNRS, Institute for Radical Chemistry, UMR 7273, 23 Av Escadrille Nomandie-Niemen, 13397, Marseille Cedex 20, France.
Université de Strasbourg, CNRS, Institut Charles Sadron UPR22, 23 rue du Loess, 67034, Strasbourg Cedex 2, France.
Angew Chem Int Ed Engl. 2021 Jan 11;60(2):917-926. doi: 10.1002/anie.202010171. Epub 2020 Nov 10.
A major step towards reliable reading of information coded in the sequence of long poly(phosphodiester)s was previously achieved by introducing an alkoxyamine spacer between information sub-segments. However, MS/MS decoding had to be performed manually to safely identify useful fragments of low abundance compared to side-products from the amide-based alkoxyamine used. Here, alternative alkoxyamines were designed to prevent side-reactions and enable automated MS/MS sequencing. Different styryl-TEMPO spacers were prepared to increase radical delocalization and stiffness of the structure. Their dissociation behavior was investigated by EPR and best results were obtained with spacers containing in-chain benzyl ring, with no side-reaction during synthesis or sequencing. Automated decoding of these polymers was performed using the MS-DECODER software, which interprets fragmentation data recorded for each sub-segment and re-align them in their original order based on location tags.
先前，通过在信息子片段之间引入烷氧基胺间隔物，朝着可靠读取长多（磷酸二酯）序列中编码的信息迈出了重要一步。然而，与酰胺基烷氧基胺的副产物相比，为了安全地鉴定低丰度的有用片段，必须手动进行 MS/MS 解码。在这里，设计了替代的烷氧基胺以防止副反应并实现自动化 MS/MS 测序。合成了不同的苯乙烯基-TEMPO 间隔物以增加自由基离域和结构的刚性。通过 EPR 研究了它们的解离行为，结果表明含有链内苄基环的间隔物效果最佳，在合成或测序过程中没有副反应。使用 MS-DECODER 软件对这些聚合物进行自动解码，该软件解释为每个子片段记录的碎片数据，并根据位置标记将它们重新排列回原始顺序。
