<p>Reliable authentication of hop (<i>Humulus lupulus</i> L.) cultivars is essential for quality control, as substantial differences in commercial value between them create a persistent risk of adulteration. A rapid and direct method for the differentiation of commercial hop cultivars has been developed based on atmospheric pressure laser plasma ionization mass spectrometry combined with unsupervised chemometric approaches. The method enables untargeted profiling of volatile organic compounds directly from hop pellets in positive-ion mode without sample preparation, with an analysis time of 3&#xa0;min per sample. The approach was validated on ten samples covering both geographically and genealogically distant and closely related cultivars originating from the same region. A graph-based data processing framework was implemented for unambiguous differentiation, integrating an unsupervised feature selection strategy based on Geary's C spatial autocorrelation index with Uniform Manifold Approximation and Projection (UMAP) visualization and Louvain clustering. It was demonstrated that features selected using five cultivars retained their discriminative ability when applied to five cultivars not involved in the selection procedure. Equivalent clustering performance was obtained on both a high-resolution Orbitrap and a lower-resolution time-of-flight mass spectrometer.</p>

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Unsupervised Differentiation of Hop Cultivars Using Atmospheric Pressure Laser Plasma Ionization Mass Spectrometry

  • K. Yu. Kravets,
  • A. A. Grechnikov,
  • O. A. Frolov

摘要

Reliable authentication of hop (Humulus lupulus L.) cultivars is essential for quality control, as substantial differences in commercial value between them create a persistent risk of adulteration. A rapid and direct method for the differentiation of commercial hop cultivars has been developed based on atmospheric pressure laser plasma ionization mass spectrometry combined with unsupervised chemometric approaches. The method enables untargeted profiling of volatile organic compounds directly from hop pellets in positive-ion mode without sample preparation, with an analysis time of 3 min per sample. The approach was validated on ten samples covering both geographically and genealogically distant and closely related cultivars originating from the same region. A graph-based data processing framework was implemented for unambiguous differentiation, integrating an unsupervised feature selection strategy based on Geary's C spatial autocorrelation index with Uniform Manifold Approximation and Projection (UMAP) visualization and Louvain clustering. It was demonstrated that features selected using five cultivars retained their discriminative ability when applied to five cultivars not involved in the selection procedure. Equivalent clustering performance was obtained on both a high-resolution Orbitrap and a lower-resolution time-of-flight mass spectrometer.