Analysis of Synthetic Monodisperse Polysaccharides by Wide Mass Range Ultrahigh-Resolution MALDI Mass Spectrometry,Analytical Chemistry

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Analysis of Synthetic Monodisperse Polysaccharides by Wide Mass Range Ultrahigh-Resolution MALDI Mass Spectrometry
Analytical Chemistry ( IF 6.7 ) Pub Date : 2021-03-05 , DOI: 10.1021/acs.analchem.1c00239
Simone Nicolardi ₁ , A Abragam Joseph ₂ , Qian Zhu ₃ , Zhengnan Shen ₄ , Alonso Pardo-Vargas _{2,

5} , Fabrizio Chiodo _{6,

7} , Antonio Molinaro ₈ , Alba Silipo ₈ , Yuri E M van der Burgt ₁ , Biao Yu _{3,

9} , Peter H Seeberger _{2,

5} , Manfred Wuhrer ₁

Affiliation

Center for Proteomics and Metabolomics, Leiden University Medical Center, Leiden 2333 ZA, The Netherlands.
Department of Biomolecular Systems, Max-Planck-Institute of Colloids and Interfaces, 14476 Potsdam, Germany.
State Key Laboratory of Bioorganic and Natural Products Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
School of Physical Science and Technology, ShanghaiTech University, 393 Huaxia Middle Road, Shanghai 201210, China.
Institute of Chemistry and Biochemistry, Freie Universität Berlin, Arnimallee 22, Berlin 14195, Germany.
Institute of Biomolecular Chemistry (ICB), Italian National Research Council (CNR), Via Campi Flegrei, 34, Pozzuoli, Napoli 80078, Italy.
Amsterdam UMC-Locatie VUMC, Molecular Cell Biology and Immunology, De Boelelaan 1108, Amsterdam 1081 HZ, The Netherlands.
Department of Chemical Sciences, University of Naples Federico II, Via Cintia 4, Napoli 80126, Italy.
School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, 1 Sub-lane Xiangshan, Hangzhou 310024, China.

Carbohydrates, such as oligo- and polysaccharides, are highly abundant biopolymers that are involved in numerous processes. The study of their structure and functions is commonly based on a material that is isolated from complex natural sources. However, a more precise analysis requires pure compounds with well-defined structures that can be obtained from chemical or enzymatic syntheses. Novel synthetic strategies have increased the accessibility of larger monodisperse polysaccharides, posing a challenge to the analytical methods used for their molecular characterization. Here, we present wide mass range ultrahigh-resolution matrix-assisted laser desorption/ionization (MALDI) Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry (MS) as a powerful platform for the analysis of synthetic oligo- and polysaccharides. Synthetic carbohydrates 16-, 64-, 100-, and 151-mers were mass analyzed and characterized by MALDI in-source decay FT-ICR MS. Detection of fragment ions generated from glycosidic bond cleavage (or cross-ring cleavage) provided information of the monosaccharide content and the linkage type, allowing for the corroboration of the carbohydrate compositions and structures.

中文翻译：

通过宽质量范围超高分辨率 MALDI 质谱分析合成单分散多糖

碳水化合物，例如寡糖和多糖，是参与许多过程的高度丰富的生物聚合物。对其结构和功能的研究通常基于从复杂的天然来源中分离出来的材料。然而，更精确的分析需要具有明确结构的纯化合物，这些化合物可以通过化学或酶合成获得。新颖的合成策略增加了较大单分散多糖的可及性，这对用于其分子表征的分析方法提出了挑战。在这里，我们提出了宽质量范围超高分辨率基质辅助激光解吸/电离 (MALDI) 傅里叶变换离子回旋共振 (FT-ICR) 质谱 (MS)，作为分析合成寡糖和多糖的强大平台。通过 MALDI 源内衰变 FT-ICR MS 对合成碳水化合物 16、64、100 和 151 聚体进行质量分析和表征。检测糖苷键裂解（或跨环裂解）产生的碎片离子提供了单糖含量和键合类型的信息，从而可以证实碳水化合物的组成和结构。

更新日期：2021-03-16

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