Differentiation of Sialyl Linkages Using a Combination of Alkyl
Esterification and Phenylhydrazine Derivatization: Application
for N-Glycan Profiling in the Sera of Patients with Lung Cancer

J 2022

Differentiation of Sialyl Linkages Using a Combination of Alkyl Esterification and Phenylhydrazine Derivatization: Application for N-Glycan Profiling in the Sera of Patients with Lung Cancer

JEŽKOVÁ, Petra, Jana SKŘIČKOVÁ, Gejza WIMMER, Jana ZELINKOVÁ, Zbyněk ZDRÁHAL et. al.

Basic information

Original name

Differentiation of Sialyl Linkages Using a Combination of Alkyl Esterification and Phenylhydrazine Derivatization: Application for N-Glycan Profiling in the Sera of Patients with Lung Cancer

Authors

JEŽKOVÁ, Petra (203 Czech Republic, belonging to the institution), Jana SKŘIČKOVÁ (203 Czech Republic), Gejza WIMMER (703 Slovakia), Jana ZELINKOVÁ (203 Czech Republic, belonging to the institution), Zbyněk ZDRÁHAL (203 Czech Republic, belonging to the institution) and Erika LATTOVÁ (703 Slovakia, guarantor, belonging to the institution)

Edition

ANALYTICAL CHEMISTRY, UNITED STATES, AMER CHEMICAL SOC, 2022, 0003-2700

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10406 Analytical chemistry

Country of publisher

United States of America

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

fulltext

Impact factor

Impact factor: 7.400

RIV identification code

RIV/00216224:14740/22:00125948

Organization unit

Central European Institute of Technology

DOI

http://dx.doi.org/10.1021/acs.analchem.2c00105

UT WoS

000798539200014

Keywords in English

Mass-spectrometric analysis; Structural-characterization; Acid derivatization; Glycosylation; Adenocarcinoma; Oligosaccharides; Stabilization; Glycoproteins

Abstract

V originále

Alterations in oligosaccharides and types of sialic acid (SA) attachments have been associated with different pathological states. Matrix-assisted laser desorption mass spectrometry (MS) is commonly used for glycosylation studies. However, native sialylated glycans are suppressed or not detected during MS experiments. Consequently, different approaches have been employed to neutralize the negative charge of the carboxyl group. In this study, we present the advantage of phenylhydrazine (PHN) labeling for the detection and efficient discrimination of SA linkages when this derivatization follows alkyl esterification. As expected, PHN-labeled sialylated oligosaccharides with the 2,6-linkage type can be easily recognized according to the additional shift in mass corresponding to the presence of a methyl or ethyl group. Surprisingly, oligosaccharides with the 2,3-linked SA residue instead of a lactone were detected carrying the second PHN unit. This was beneficial as no further processing after esterification was needed to stabilize the lactone form. Moreover, during tandem mass experiments, all modified glycans produced favorable fragmentation patterns with a coherent recognition of SA linkages. Although both types of esterification, herein called the EST-PHN approach, provided comparable results, methylation exhibited marginally higher linkage specificity than ethyl esterification. The simplicity and effectiveness of the methodology are demonstrated on the model compound, sialyllactose, and its applicability for biological studies is presented on N-glycan profiling in the sera of lung cancer patients.

Links

EF18_046/0015974, research and development project

Name: Modernizace České infrastruktury pro integrativní strukturní biologii

90127, large research infrastructures

Name: CIISB II

Citovat

JEŽKOVÁ, Petra, Jana SKŘIČKOVÁ, Gejza WIMMER, Jana ZELINKOVÁ, Zbyněk ZDRÁHAL and Erika LATTOVÁ. Differentiation of Sialyl Linkages Using a Combination of Alkyl Esterification and Phenylhydrazine Derivatization: Application for N-Glycan Profiling in the Sera of Patients with Lung Cancer. ANALYTICAL CHEMISTRY. UNITED STATES: AMER CHEMICAL SOC, 2022, vol. 94, No 18, p. 6736-6744. ISSN 0003-2700. Available from: https://dx.doi.org/10.1021/acs.analchem.2c00105.

@article{1858721,
   author = {Ježková, Petra and Skřičková, Jana and Wimmer, Gejza and Zelinková, Jana and Zdráhal, Zbyněk and Lattová, Erika},
   article_location = {UNITED STATES},
   article_number = {18},
   doi = {http://dx.doi.org/10.1021/acs.analchem.2c00105},
   keywords = {Mass-spectrometric analysis; Structural-characterization; Acid derivatization; Glycosylation; Adenocarcinoma; Oligosaccharides; Stabilization; Glycoproteins},
   language = {eng},
   issn = {0003-2700},
   journal = {ANALYTICAL CHEMISTRY},
   title = {Differentiation of Sialyl Linkages Using a Combination of Alkyl Esterification and Phenylhydrazine Derivatization: Application for N-Glycan Profiling in the Sera of Patients with Lung Cancer},
   url = {https://pubs.acs.org/doi/10.1021/acs.analchem.2c00105},
   volume = {94},
   year = {2022}
}

TY  - JOUR
ID  - 1858721
AU  - Ježková, Petra - Skřičková, Jana - Wimmer, Gejza - Zelinková, Jana - Zdráhal, Zbyněk - Lattová, Erika
PY  - 2022
TI  - Differentiation of Sialyl Linkages Using a Combination of Alkyl Esterification and Phenylhydrazine Derivatization: Application for N-Glycan Profiling in the Sera of Patients with Lung Cancer
JF  - ANALYTICAL CHEMISTRY
VL  - 94
IS  - 18
SP  - 6736-6744
EP  - 6736-6744
PB  - AMER CHEMICAL SOC
SN  - 00032700
KW  - Mass-spectrometric analysis
KW  - Structural-characterization
KW  - Acid derivatization
KW  - Glycosylation
KW  - Adenocarcinoma
KW  - Oligosaccharides
KW  - Stabilization
KW  - Glycoproteins
UR  - https://pubs.acs.org/doi/10.1021/acs.analchem.2c00105
N2  - Alterations in oligosaccharides and types of sialic acid (SA) attachments have been associated with different pathological states. Matrix-assisted laser desorption mass spectrometry (MS) is commonly used for glycosylation studies. However, native sialylated glycans are suppressed or not detected during MS experiments. Consequently, different approaches have been employed to neutralize the negative charge of the carboxyl group. In this study, we present the advantage of phenylhydrazine (PHN) labeling for the detection and efficient discrimination of SA linkages when this derivatization follows alkyl esterification. As expected, PHN-labeled sialylated oligosaccharides with the 2,6-linkage type can be easily recognized according to the additional shift in mass corresponding to the presence of a methyl or ethyl group. Surprisingly, oligosaccharides with the 2,3-linked SA residue instead of a lactone were detected carrying the second PHN unit. This was beneficial as no further processing after esterification was needed to stabilize the lactone form. Moreover, during tandem mass experiments, all modified glycans produced favorable fragmentation patterns with a coherent recognition of SA linkages. Although both types of esterification, herein called the EST-PHN approach, provided comparable results, methylation exhibited marginally higher linkage specificity than ethyl esterification. The simplicity and effectiveness of the methodology are demonstrated on the model compound, sialyllactose, and its applicability for biological studies is presented on N-glycan profiling in the sera of lung cancer patients.
ER  -

JEŽKOVÁ, Petra, Jana SKŘIČKOVÁ, Gejza WIMMER, Jana ZELINKOVÁ, Zbyněk ZDRÁHAL and Erika LATTOVÁ. Differentiation of Sialyl Linkages Using a Combination of Alkyl Esterification and Phenylhydrazine Derivatization: Application for N-Glycan Profiling in the Sera of Patients with Lung Cancer. \textit{ANALYTICAL CHEMISTRY}. UNITED STATES: AMER CHEMICAL SOC, 2022, vol.~94, No~18, p.~6736-6744. ISSN~0003-2700. Available from: https://dx.doi.org/10.1021/acs.analchem.2c00105.

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