Immunoglobulin A carries sulfated and O-acetylated N-glycans primarily at the tailpiece site – strategies for site-specific N-glycan identification

Sulfated N-glycans from human immunoglobulin A (IgA) were recently discovered via glycomic approaches. However, their site-specific description is still pending. Certain N-glycan structures at specific N-glycosylation sites in IgA are crucial for microbial neutralization and effector functions. For...

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Main Authors: Frania J. Zuniga-Banuelos, Greta Lemke, Marcus Hoffmann, Udo Reichl, Erdmann Rapp
Format: Article
Language:English
Published: Frontiers Media S.A. 2025-08-01
Series:Frontiers in Molecular Biosciences
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Online Access:https://www.frontiersin.org/articles/10.3389/fmolb.2025.1595173/full
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author Frania J. Zuniga-Banuelos
Frania J. Zuniga-Banuelos
Greta Lemke
Greta Lemke
Marcus Hoffmann
Udo Reichl
Udo Reichl
Erdmann Rapp
Erdmann Rapp
author_facet Frania J. Zuniga-Banuelos
Frania J. Zuniga-Banuelos
Greta Lemke
Greta Lemke
Marcus Hoffmann
Udo Reichl
Udo Reichl
Erdmann Rapp
Erdmann Rapp
author_sort Frania J. Zuniga-Banuelos
collection DOAJ
description Sulfated N-glycans from human immunoglobulin A (IgA) were recently discovered via glycomic approaches. However, their site-specific description is still pending. Certain N-glycan structures at specific N-glycosylation sites in IgA are crucial for microbial neutralization and effector functions. For instance, sialylated N-glycans on the C-terminal tailpiece mediate anti-viral activity by interfering with sialic-acid-binding viruses. Sulfated N-glycan epitopes can be ligands for viral proteins and thus play a role in the immune response. In this study, we performed a site-specific screening for sulfated and other rare N-glycans in two commercially available human serum IgA samples employing an in-depth N-glycoproteomic approach, previously developed by us. We found evidence of complex-type and hybrid-type N-glycans containing sulfated N-acetylhexosamine (sulfated HexNAc) attached to the N-glycosylation sites in the tailpiece and the CH2 domain of both IgA subclasses. Also, complex-type N-glycan compositions bearing O-acetylated sialic acid were identified primarily at the tailpiece site. Surprisingly, N-glycans bearing glucuronic acid were identified in the commercial IgA samples, but from peptides of “contaminant” glycoproteins. A detailed comparison of the N-glycosylation profiles of human serum IgA samples from two suppliers showed such N-glycans with sulfated HexNAc consistently in higher abundance in the tailpiece region. These findings have not been described before for a site-specific glycopeptide analysis. Overall, our work provides strategies for performing a dedicated site-specific search for sulfated and O-acetylated N-glycans that can be easily transferred, e.g., to human IgA derived from mucosal tissues, milk, or saliva. We expect that a wider and deeper micro-heterogeneity description of clinically relevant glycoproteins, such as immunoglobulins, can expand the screening for biomarkers or treatment options.
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publisher Frontiers Media S.A.
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series Frontiers in Molecular Biosciences
spelling doaj-art-c40c85435cfa43d88dc6e2e4186205402025-08-20T03:16:03ZengFrontiers Media S.A.Frontiers in Molecular Biosciences2296-889X2025-08-011210.3389/fmolb.2025.15951731595173Immunoglobulin A carries sulfated and O-acetylated N-glycans primarily at the tailpiece site – strategies for site-specific N-glycan identificationFrania J. Zuniga-Banuelos0Frania J. Zuniga-Banuelos1Greta Lemke2Greta Lemke3Marcus Hoffmann4Udo Reichl5Udo Reichl6Erdmann Rapp7Erdmann Rapp8Bioprocess Engineering, Max Planck Institute for Dynamics of Complex Technical Systems, Magdeburg, GermanyglyXera GmbH, Magdeburg, GermanyBioprocess Engineering, Max Planck Institute for Dynamics of Complex Technical Systems, Magdeburg, GermanyBioprocess Engineering, Otto von Guericke University Magdeburg, Magdeburg, GermanyBioprocess Engineering, Max Planck Institute for Dynamics of Complex Technical Systems, Magdeburg, GermanyBioprocess Engineering, Max Planck Institute for Dynamics of Complex Technical Systems, Magdeburg, GermanyBioprocess Engineering, Otto von Guericke University Magdeburg, Magdeburg, GermanyBioprocess Engineering, Max Planck Institute for Dynamics of Complex Technical Systems, Magdeburg, GermanyglyXera GmbH, Magdeburg, GermanySulfated N-glycans from human immunoglobulin A (IgA) were recently discovered via glycomic approaches. However, their site-specific description is still pending. Certain N-glycan structures at specific N-glycosylation sites in IgA are crucial for microbial neutralization and effector functions. For instance, sialylated N-glycans on the C-terminal tailpiece mediate anti-viral activity by interfering with sialic-acid-binding viruses. Sulfated N-glycan epitopes can be ligands for viral proteins and thus play a role in the immune response. In this study, we performed a site-specific screening for sulfated and other rare N-glycans in two commercially available human serum IgA samples employing an in-depth N-glycoproteomic approach, previously developed by us. We found evidence of complex-type and hybrid-type N-glycans containing sulfated N-acetylhexosamine (sulfated HexNAc) attached to the N-glycosylation sites in the tailpiece and the CH2 domain of both IgA subclasses. Also, complex-type N-glycan compositions bearing O-acetylated sialic acid were identified primarily at the tailpiece site. Surprisingly, N-glycans bearing glucuronic acid were identified in the commercial IgA samples, but from peptides of “contaminant” glycoproteins. A detailed comparison of the N-glycosylation profiles of human serum IgA samples from two suppliers showed such N-glycans with sulfated HexNAc consistently in higher abundance in the tailpiece region. These findings have not been described before for a site-specific glycopeptide analysis. Overall, our work provides strategies for performing a dedicated site-specific search for sulfated and O-acetylated N-glycans that can be easily transferred, e.g., to human IgA derived from mucosal tissues, milk, or saliva. We expect that a wider and deeper micro-heterogeneity description of clinically relevant glycoproteins, such as immunoglobulins, can expand the screening for biomarkers or treatment options.https://www.frontiersin.org/articles/10.3389/fmolb.2025.1595173/fullimmunoglobulin A (IgA)mass spectrometryglycoproteomicsN-glycosylationoxonium marker ionssulfated N-glycans
spellingShingle Frania J. Zuniga-Banuelos
Frania J. Zuniga-Banuelos
Greta Lemke
Greta Lemke
Marcus Hoffmann
Udo Reichl
Udo Reichl
Erdmann Rapp
Erdmann Rapp
Immunoglobulin A carries sulfated and O-acetylated N-glycans primarily at the tailpiece site – strategies for site-specific N-glycan identification
Frontiers in Molecular Biosciences
immunoglobulin A (IgA)
mass spectrometry
glycoproteomics
N-glycosylation
oxonium marker ions
sulfated N-glycans
title Immunoglobulin A carries sulfated and O-acetylated N-glycans primarily at the tailpiece site – strategies for site-specific N-glycan identification
title_full Immunoglobulin A carries sulfated and O-acetylated N-glycans primarily at the tailpiece site – strategies for site-specific N-glycan identification
title_fullStr Immunoglobulin A carries sulfated and O-acetylated N-glycans primarily at the tailpiece site – strategies for site-specific N-glycan identification
title_full_unstemmed Immunoglobulin A carries sulfated and O-acetylated N-glycans primarily at the tailpiece site – strategies for site-specific N-glycan identification
title_short Immunoglobulin A carries sulfated and O-acetylated N-glycans primarily at the tailpiece site – strategies for site-specific N-glycan identification
title_sort immunoglobulin a carries sulfated and o acetylated n glycans primarily at the tailpiece site strategies for site specific n glycan identification
topic immunoglobulin A (IgA)
mass spectrometry
glycoproteomics
N-glycosylation
oxonium marker ions
sulfated N-glycans
url https://www.frontiersin.org/articles/10.3389/fmolb.2025.1595173/full
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