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离去基团非对应异构体对保护型半乳糖苷糖阳离子结构的影响。

The Impact of Leaving Group Anomericity on the Structure of Glycosyl Cations of Protected Galactosides.

机构信息

Institute of Chemistry and Biochemistry, Freie Universität Berlin, Arnimallee 22, 14195, Berlin, Germany.

Department of Molecular Physics, Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, 14195, Berlin, Germany.

出版信息

Chemphyschem. 2020 Sep 2;21(17):1905-1907. doi: 10.1002/cphc.202000473. Epub 2020 Jul 30.

DOI:10.1002/cphc.202000473
PMID:32652759
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7540451/
Abstract

It has been reported that fragments produced by glycosidic bond breakage in mass spectrometry-based experiments can retain a memory of their anomeric configuration, which has major implications for glycan sequencing. Herein, we use cryogenic vibrational spectroscopy and ion mobility-mass spectrometry to study the structure of B-type fragments of protected galactosides. Cationic fragments were generated from glycosyl donors carrying trichloroacetimidate or thioethyl leaving groups of different anomeric configuration. The obtained infrared signatures indicate that the investigated fragments exhibit an identical structure, which suggests that there is no anomeric memory in B-type ions of fully protected monosaccharides.

摘要

据报道,在基于质谱的实验中,糖苷键断裂产生的碎片可以保留其端基构型的记忆,这对聚糖测序有重大影响。在此,我们使用低温振动光谱和离子淌度-质谱研究了保护型半乳糖苷的 B 型片段的结构。带有三氯乙酰亚胺酯或硫代乙基离去基团的不同端基构型的糖基供体生成了阳离子片段。得到的红外特征表明,所研究的片段表现出相同的结构,这表明完全保护的单糖的 B 型离子中没有端基构型记忆。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1991/7540451/8585362b42f2/CPHC-21-1905-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1991/7540451/8377b0163279/CPHC-21-1905-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1991/7540451/06492ae1b2b2/CPHC-21-1905-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1991/7540451/8585362b42f2/CPHC-21-1905-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1991/7540451/8377b0163279/CPHC-21-1905-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1991/7540451/06492ae1b2b2/CPHC-21-1905-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1991/7540451/8585362b42f2/CPHC-21-1905-g002.jpg

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