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Global metabolomics profiling of glucuronides in human plasma, fecal, and cerebrospinal fluid samples

Tsiara, Ioanna ; Correia, Mario S.P. ; Yang, Fan ; Zeng, Weiming ; Seeburger, Pauline ; Hervás Povo, Belén ; Lundgaard, Iben LU ; Menéndez-González, Manuel ; Vujasinovic, Miroslav and Löhr, J. Matthias , et al. (2025) In Analytical and Bioanalytical Chemistry
Abstract

Glucuronidation is the major phase II biotransformation reaction that facilitates the clearance of exogenous compounds from the human body. Glucuronidated metabolites have been investigated in urine samples at a broad scale; however, their characterization in other human biospecimens is underexplored. Our study has now performed a comprehensive profiling of glucuronides in plasma, fecal, and cerebrospinal fluid (CSF) of humans. We performed a mass spectrometry-based analysis that combines enzymatic hydrolysis with a β-glucuronidase to selectively cleave the glucuronic acid moiety, a developed in-house glucuronide identification pipeline, and enzymatic synthesis of standard metabolites. In total, we identified 32 glucuronidated... (More)

Glucuronidation is the major phase II biotransformation reaction that facilitates the clearance of exogenous compounds from the human body. Glucuronidated metabolites have been investigated in urine samples at a broad scale; however, their characterization in other human biospecimens is underexplored. Our study has now performed a comprehensive profiling of glucuronides in plasma, fecal, and cerebrospinal fluid (CSF) of humans. We performed a mass spectrometry-based analysis that combines enzymatic hydrolysis with a β-glucuronidase to selectively cleave the glucuronic acid moiety, a developed in-house glucuronide identification pipeline, and enzymatic synthesis of standard metabolites. In total, we identified 32 glucuronidated metabolites across the three sample types in both negative and positive mass spectrometry ionization modes using advanced MS/MS fragmentation analysis. We have utilized a straightforward enzymatic synthesis of glucuronidated metabolites for annotation at the highest confidence level. Among the identified conjugates, we detected glucuronides of different compound classes including drugs, bile acid derivatives, steroid conjugates, and phenolic compounds. Unexpectedly, we validated the glucuronides of acetaminophen and propofol in CSF samples, the latter representing a novel observation that highlights the importance of investigating phase II metabolites in uncommon sample types.

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organization
publishing date
type
Contribution to journal
publication status
epub
subject
keywords
Enzymatic synthesis, Glucuronides, Gut microbiota, Metabolomics, Phase II modifications
in
Analytical and Bioanalytical Chemistry
publisher
Springer Science and Business Media B.V.
external identifiers
  • scopus:105014868909
ISSN
1618-2642
DOI
10.1007/s00216-025-06082-w
language
English
LU publication?
yes
id
1159cc90-4789-4586-8f40-4109a2076c61
date added to LUP
2025-11-17 09:11:05
date last changed
2025-11-17 09:12:15
@article{1159cc90-4789-4586-8f40-4109a2076c61,
  abstract     = {{<p>Glucuronidation is the major phase II biotransformation reaction that facilitates the clearance of exogenous compounds from the human body. Glucuronidated metabolites have been investigated in urine samples at a broad scale; however, their characterization in other human biospecimens is underexplored. Our study has now performed a comprehensive profiling of glucuronides in plasma, fecal, and cerebrospinal fluid (CSF) of humans. We performed a mass spectrometry-based analysis that combines enzymatic hydrolysis with a β-glucuronidase to selectively cleave the glucuronic acid moiety, a developed in-house glucuronide identification pipeline, and enzymatic synthesis of standard metabolites. In total, we identified 32 glucuronidated metabolites across the three sample types in both negative and positive mass spectrometry ionization modes using advanced MS/MS fragmentation analysis. We have utilized a straightforward enzymatic synthesis of glucuronidated metabolites for annotation at the highest confidence level. Among the identified conjugates, we detected glucuronides of different compound classes including drugs, bile acid derivatives, steroid conjugates, and phenolic compounds. Unexpectedly, we validated the glucuronides of acetaminophen and propofol in CSF samples, the latter representing a novel observation that highlights the importance of investigating phase II metabolites in uncommon sample types.</p>}},
  author       = {{Tsiara, Ioanna and Correia, Mario S.P. and Yang, Fan and Zeng, Weiming and Seeburger, Pauline and Hervás Povo, Belén and Lundgaard, Iben and Menéndez-González, Manuel and Vujasinovic, Miroslav and Löhr, J. Matthias and Globisch, Daniel}},
  issn         = {{1618-2642}},
  keywords     = {{Enzymatic synthesis; Glucuronides; Gut microbiota; Metabolomics; Phase II modifications}},
  language     = {{eng}},
  publisher    = {{Springer Science and Business Media B.V.}},
  series       = {{Analytical and Bioanalytical Chemistry}},
  title        = {{Global metabolomics profiling of glucuronides in human plasma, fecal, and cerebrospinal fluid samples}},
  url          = {{http://dx.doi.org/10.1007/s00216-025-06082-w}},
  doi          = {{10.1007/s00216-025-06082-w}},
  year         = {{2025}},
}