Cryogenic Infrared Spectroscopy Reveals Structural Modularity in the Vibrational Fingerprints of Heparan Sulfate Diastereomers.,Analytical Chemistry

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Cryogenic Infrared Spectroscopy Reveals Structural Modularity in the Vibrational Fingerprints of Heparan Sulfate Diastereomers.
Analytical Chemistry ( IF 6.7 ) Pub Date : 2020-07-13 , DOI: 10.1021/acs.analchem.0c02048
Maike Lettow _{1,

2} , Márkó Grabarics _{1,

2} , Kim Greis _{1,

2} , Eike Mucha ₁ , Daniel A Thomas ₁ , Pradeep Chopra ₃ , Geert-Jan Boons _{3,

4} , Richard Karlsson ₅ , Jeremy E Turnbull _{5,

6} , Gerard Meijer ₁ , Rebecca L Miller ₅ , Gert von Helden ₁ , Kevin Pagel _{1,

2}

Affiliation

Heparan sulfate and heparin are highly acidic polysaccharides with a linear sequence, consisting of alternating glucosamine and hexuronic acid building blocks. The identity of hexuronic acid units shows a variability along their sequence, as d-glucuronic acid and its C5 epimer, l-iduronic acid, can both occur. The resulting backbone diversity represents a major challenge for an unambiguous structural assignment by mass spectrometry-based techniques. Here, we employ cryogenic infrared spectroscopy on mass-selected ions to overcome this challenge and distinguish isomeric heparan sulfate tetrasaccharides that differ only in the configuration of their hexuronic acid building blocks. High-resolution infrared spectra of a systematic set of synthetic heparan sulfate stereoisomers were recorded in the fingerprint region from 1000 to 1800 cm^–1. The experiments reveal a characteristic combination of spectral features for each of the four diastereomers studied and imply structural modularity in the vibrational fingerprints. Strong spectrum-structure correlations were found and rationalized by state-of-the-art quantum chemical calculations. The findings demonstrate the potential of cryogenic infrared spectroscopy to extend the mass spectrometry-based toolkit for the sequencing of heparan sulfate and structurally related biomolecules.

中文翻译：

低温红外光谱揭示了硫酸乙酰肝素非对映异构体振动指纹中的结构模块化。

硫酸乙酰肝素和肝素是具有线性序列的强酸性多糖，由交替的氨基葡萄糖和己糖醛酸结构单元组成。己糖醛酸单元的特性显示出其序列的可变性，如d-葡萄糖醛酸及其C 5 差向异构体，l-艾杜糖醛酸，两者都可能发生。由此产生的主干多样性代表了基于质谱技术的明确结构分配的主要挑战。在这里，我们对质量选择的离子采用低温红外光谱来克服这一挑战，并区分仅在其己糖醛酸结构单元的配置上不同的异构硫酸乙酰肝素四糖。^{在 1000 至 1800 cm –1}的指纹区域中记录了一组系统的合成硫酸乙酰肝素立体异构体的高分辨率红外光谱. 实验揭示了所研究的四种非对映异构体中每一种的光谱特征的特征组合，并暗示了振动指纹中的结构模块化。通过最先进的量子化学计算发现并合理化了强烈的光谱结构相关性。这些发现证明了低温红外光谱在扩展基于质谱的工具包以对硫酸乙酰肝素和结构相关的生物分子进行测序方面的潜力。

更新日期：2020-08-04

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