Forward-predictive SERS-based chemical taxonomy for untargeted structural elucidation of epimeric cerebrosides.
Emily Xi TanShi Xuan LeongWei An LiewIn Yee PhangAlice Ng Jie YingNguan Soon TanYie Hou LeeXing Yi LingPublished in: Nature communications (2024)
Achieving untargeted chemical identification, isomeric differentiation, and quantification is critical to most scientific and technological problems but remains challenging. Here, we demonstrate an integrated SERS-based chemical taxonomy machine learning framework for untargeted structural elucidation of 11 epimeric cerebrosides, attaining >90% accuracy and robust single epimer and multiplex quantification with <10% errors. First, we utilize 4-mercaptophenylboronic acid to selectively capture the epimers at molecular sites of isomerism to form epimer-specific SERS fingerprints. Corroborating with in-silico experiments, we establish five spectral features, each corresponding to a structural characteristic: (1) presence/absence of epimers, (2) monosaccharide/cerebroside, (3) saturated/unsaturated cerebroside, (4) glucosyl/galactosyl, and (5) GlcCer or GalCer's carbon chain lengths. Leveraging these insights, we create a fully generalizable framework to identify and quantify cerebrosides at concentrations between 10 -4 to 10 -10 M and achieve multiplex quantification of binary mixtures containing biomarkers GlcCer 24:1 , and GalCer 24:1 using their untrained spectra in the models.
Keyphrases
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