Simplifying PA Quantification: A Unified Enrichment and Reduction Workflow for Retronecine-Based Quantification of Pyrrolizidine Alkaloids in Phyto Samples
- 1ADSI—Austrian Drug Screening Institute GmbH, University of Innsbruck, Mitterweg 24, 6020 Innsbruck, Austria
- 2Institute of Analytical Chemistry and Radiochemistry, CCB—Center for Chemistry and Biomedicine, Leopold-Franzens University, Innrain 80/82, 6020 Innsbruck, Austria
- 3Bionorica SE, Kerschensteinerstraße 11–15, 92318 Neumarkt, Germany
Abstract
Pyrrolizidine alkaloids (PAs) are a chemically diverse group of plant-derived toxins whose quantification in botanical materials remains analytically challenging. This study integrates previously established nano zirconium silicate (NZS) enrichment with one-pot lithium aluminium hydride reduction/hydrolysis and LC–HRMS determination of the resulting necine-base response. The workflow targets retronecine- and heliotridine-type PAs and their N-oxides, with results expressed as retronecine equivalents. In Radix Primulae, three independent samples were spiked at each of 200, 250 and 300 µg/kg retronecine equivalents and processed through the complete analytical workflow. Mean recoveries were 83.0%, 94.2% and 92.5%, with between-preparation RSDs of 3.12%, 1.55% and 1.96%, respectively. Matrix-matched regression was evaluated using six calibration levels (10, 100, 200, 300, 400, 500; Day-1 R2 = 0.99936). Calculated Day-1 LOD and LOQ estimates were 14.94 and 45.27 µg/L. Remeasurement of the same extracts after 24 h, using a separate daily calibration, gave paired concentration changes of −0.67% to +1.23%. Application to a naturally contaminated comfrey sample demonstrated the workflow’s applicability beyond spiked samples, with agreement between the conversion-based result and the summed intact-PA reference approach.
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BibTeX
@article{schwarz2026simplifying,
title = {{Simplifying PA Quantification: A Unified Enrichment and Reduction Workflow for Retronecine-Based Quantification of Pyrrolizidine Alkaloids in Phyto Samples}},
author = {Benedikt Schwarz and Thomas Jakschitz and Christian W. Huck and Moritz Rubner and Michael Popp and Günther K. Bonn},
journal = {Molecules},
year = {2026},
month = oct,
doi = {10.3390/molecules31203590},
url = {https://www.mdpi.com/1420-3049/31/20/3590},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Simplifying PA Quantification: A Unified Enrichment and Reduction Workflow for Retronecine-Based Quantification of Pyrrolizidine Alkaloids in Phyto Samples
AU - Benedikt Schwarz
AU - Thomas Jakschitz
AU - Christian W. Huck
AU - Moritz Rubner
AU - Michael Popp
AU - Günther K. Bonn
PY - 2026
DA - 2026/10/01
JO - Molecules
DO - 10.3390/molecules31203590
UR - https://www.mdpi.com/1420-3049/31/20/3590
AB - Pyrrolizidine alkaloids (PAs) are a chemically diverse group of plant-derived toxins whose quantification in botanical materials remains analytically challenging. This study integrates previously established nano zirconium silicate (NZS) enrichment with one-pot lithium aluminium hydride reduction/hydrolysis and LC–HRMS determination of the resulting necine-base response. The workflow targets retronecine- and heliotridine-type PAs and their N-oxides, with results expressed as retronecine equivalents. In Radix Primulae, three independent samples were spiked at each of 200, 250 and 300 µg/kg retronecine equivalents and processed through the complete analytical workflow. Mean recoveries were 83.0%, 94.2% and 92.5%, with between-preparation RSDs of 3.12%, 1.55% and 1.96%, respectively. Matrix-matched regression was evaluated using six calibration levels (10, 100, 200, 300, 400, 500; Day-1 R2 = 0.99936). Calculated Day-1 LOD and LOQ estimates were 14.94 and 45.27 µg/L. Remeasurement of the same extracts after 24 h, using a separate daily calibration, gave paired concentration changes of −0.67% to +1.23%. Application to a naturally contaminated comfrey sample demonstrated the workflow’s applicability beyond spiked samples, with agreement between the conversion-based result and the summed intact-PA reference approach.
SN - 1420-3049
ER -