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Systematic isolation and structure elucidation of urinary metabolites optimized for the analytical-scale molecular profiling laboratory
Journal article   Open access   Peer reviewed

Systematic isolation and structure elucidation of urinary metabolites optimized for the analytical-scale molecular profiling laboratory

L. Whiley, E. Chekmeneva, D.J. Berry, B. Jiménez, A.H.Y. Yuen, A. Salam, H. Hussain, M. Witt, Z. Takats, J. Nicholson, …
Analytical Chemistry, Vol.91(14), pp.8873-8882
2019
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Abstract

Annotation and identification of metabolite biomarkers is critical for their biological interpretation in metabolic phenotyping studies, presenting a significant bottleneck in the successful implementation of untargeted metabolomics. Here, a systematic multistep protocol was developed for the purification and de novo structural elucidation of urinary metabolites. The protocol is most suited for instances where structure elucidation and metabolite annotation are critical for the downstream biological interpretation of metabolic phenotyping studies. First, a bulk urine pool was desalted using ion-exchange resins enabling large-scale fractionation using precise iterations of analytical scale chromatography. Primary urine fractions were collected and assembled into a “fraction bank” suitable for long-term laboratory storage. Secondary and tertiary fractionations exploited differences in selectivity across a range of reversed-phase chemistries, achieving the purification of metabolites of interest yielding an amount of material suitable for chemical characterization. To exemplify the application of the systematic workflow in a diverse set of cases, four metabolites with a range of physicochemical properties were selected and purified from urine and subjected to chemical formula and structure elucidation by respective magnetic resonance mass spectrometry (MRMS) and NMR analyses. Their structures were fully assigned as tetrahydropentoxyline, indole-3-acetic-acid-O-glucuronide, p-cresol glucuronide, and pregnanediol-3-glucuronide. Unused effluent was collected, dried, and returned to the fraction bank, demonstrating the viability of the system for repeat use in metabolite annotation with a high degree of efficiency.

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Collaboration types
Industry collaboration
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Citation topics
2 Chemistry
2.211 Mass Spectrometry
2.211.990 Metabolomics
Web Of Science research areas
Chemistry, Analytical
ESI research areas
Chemistry
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