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Discriminative and quantitative analysis of norepinephrine and epinephrine by surface-enhanced Raman spectroscopy with gold nanoparticle suspensions

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Abstract

Surface-enhanced Raman spectroscopy (SERS) is a powerful analytical technique capable of increasing the Raman signal of an analyte using specific nanostructures. The close contact between those nanostructures, usually a suspension of nanoparticles, and the molecule of interest produces an important exaltation of the intensity of the Raman signal. Even if the exaltation leads to an improvement of Raman spectroscopy sensitivity, the complexity of the SERS signal and the numbers of parameters to be controlled allow the use of SERS for detection rather than quantification. The aim of this study was to develop a robust discriminative and quantitative analysis in accordance with pharmaceutical standards. In this present work, we develop a discriminative and quantitative analysis based on the previous optimized parameters obtained by the design of experiments fixed for norepinephrine (NOR) and extended to epinephrine (EPI) which are two neurotransmitters with very similar structures. Studying the short evolution of the Raman signal intensity over time coupled with chemometric tools allowed the identification of outliers and their removal from the data set. The discriminant analysis showed an excellent separation of EPI and NOR. The comparative analysis of the data showed the superiority of the multivariate analysis after logarithmic transformation. The quantitative analysis allowed the development of robust quantification models from several gold nanoparticle batches with limits of quantification of 32 µg/mL for NOR and below 20 µg/mL for EPI even though no Raman signal is observable for such concentrations. This study improves SERS analysis over ultrasensitive detection for discrimination and quantification using a handheld Raman spectrometer.

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Acknowledgements

The authors would like to acknowledge financial support for a Nan’eau microscope from Ecole Polytechnique, IDEX Paris-Saclay, Equipex Morphoscope 2, and DGA. They also thank the “Centre Interdisciplinaire de Microscopie électronique de l’X” (CIMEX). Finally, they are grateful to the Fondation ARC (French foundation for cancer research) for the financial support to Marion Berge.

Funding

This work has been supported by the Fondation ARC pour la recherche.

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Authors and Affiliations

  1. Service de Pharmacie, Hôpital européen Georges Pompidou, APHP.Centre Université-Paris, 20 rue Leblanc, 75015, Paris, France

    Antoine Dowek, Marion Berge, Patrice Prognon, Laetitia Minh Mai Lê & Eric Caudron

  2. Lipides, Systèmes Analytiques et Biologiques, Université Paris-Saclay, 92296, Châtenay-Malabry, France

    Antoine Dowek, Marion Berge, Patrice Prognon, Ali Tfayli, Laetitia Minh Mai Lê & Eric Caudron

  3. CNRS, Institut Galien Paris Sud, Université Paris-Saclay, 92296, Châtenay-Malabry, France

    François-Xavier Legrand

  4. Laboratoire de Physique de la Matière Condensée (LPMC), Ecole Polytechnique, CNRS, Institut Polytechnique de Paris, 91128, Palaiseau, France

    Eric Larquet

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  1. Antoine Dowek
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Correspondence to Antoine Dowek.

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Dowek, A., Berge, M., Prognon, P. et al. Discriminative and quantitative analysis of norepinephrine and epinephrine by surface-enhanced Raman spectroscopy with gold nanoparticle suspensions. Anal Bioanal Chem 414, 1163–1176 (2022). https://doi.org/10.1007/s00216-021-03743-4

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