Gesellschaft zur Förderung der Analytischen Wissenschaften e.V., ISAS-Leibniz Institute for Analytical Sciences, Otto-Hahn-Str. 6b, 44227, Dortmund, Germany.
Complex Carbohydrate Research Center, University of Georgia, 315 Riverbend Rd, Athens, GA, 30602, USA.
Chemistry. 2017 Mar 8;23(14):3466-3473. doi: 10.1002/chem.201605627. Epub 2017 Feb 16.
Mammalian protein O-mannosylation, initiated by attachment of α-mannopyranose to Ser or Thr residues, comprise a group of post-translational modifications (PTMs) involved in muscle and brain development. Recent advances in glycoproteomics methodology and the "SimpleCell" strategy have enabled rapid identification of glycoproteins and specific glycosylation sites. Despite the enormous progress made, the biological impact of the mammalian O-mannosyl glycoproteome remains largely unknown to date. Tools are still needed to investigate the structure, role, and abundance of O-mannosyl glycans. Although O-mannosyl branching has been shown to be of relevance in integrin-dependent cell migration, and also plays a role in demyelinating diseases, such as multiple sclerosis, a broader understanding of the biological roles of branched O-mannosyl glycans is lacking in part due to the paucity of detection tools. In this work, a glycopeptide vaccine construct was synthesized and used to generate antibodies against branched O-mannosyl glycans. Glycopeptide microarray screening revealed high selectivity of the induced antibodies for branched glycan core structures presented on different peptide backbones, with no cross-reactivity observed with related linear glycans. For comparison, microarray screening of the mannose-binding lectin concanavalin A (ConA), which is commonly used in glycoproteomics workflows to enrich tryptic O-mannosyl peptides, showed that the ConA lectin did not recognize branched O-mannosyl glycans. The binding preference of ConA for short linear O-mannosyl glycans was rationalized in terms of molecular structure using crystallographic data augmented by molecular modeling. The contrast between the ConA binding specificity and that of the new antibodies indicates a novel role for the antibodies in studies of protein O-mannosylation.
哺乳动物蛋白 O-甘露糖基化,由α-甘露糖吡喃糖基附着于丝氨酸或苏氨酸残基启动,是一组参与肌肉和大脑发育的翻译后修饰(PTMs)。糖蛋白质组学方法和“SimpleCell”策略的最新进展使得糖蛋白和特定糖基化位点的快速鉴定成为可能。尽管已经取得了巨大的进展,但哺乳动物 O-甘露糖基糖蛋白组的生物学影响迄今为止在很大程度上仍然未知。仍需要工具来研究 O-甘露糖基聚糖的结构、作用和丰度。尽管已经表明 O-甘露糖基分支在整合素依赖性细胞迁移中具有相关性,并且在脱髓鞘疾病(如多发性硬化症)中也起作用,但由于缺乏检测工具,部分原因是对分支 O-甘露糖基聚糖的生物学作用的理解还不够广泛。在这项工作中,合成了一种糖肽疫苗构建体,并用于生成针对分支 O-甘露糖基聚糖的抗体。糖肽微阵列筛选显示,诱导的抗体对不同肽骨架上呈现的分支聚糖核心结构具有高选择性,并且与相关的线性聚糖没有观察到交叉反应。相比之下,甘露糖结合凝集素伴刀豆球蛋白 A(ConA)的微阵列筛选显示,ConA 凝集素不能识别分支 O-甘露糖基聚糖。ConA 对短线性 O-甘露糖基聚糖的结合偏好根据晶体学数据和分子建模进行了分子结构的合理化。ConA 结合特异性与新抗体之间的对比表明,这些新抗体在研究蛋白质 O-甘露糖基化方面具有新的作用。