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Silver nanoflower-coated paper as dual substrate for surface-enhanced Raman spectroscopy and ambient pressure mass spectrometry analysis

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Abstract

Paper-based analytical devices (PADs) have encountered a wealth of applications in recent years thanks to the numerous advantages of paper as a support. A silver nanoflower (AgNF) modified paper-based dual substrate for both surface-enhanced Raman spectroscopy (SERS) and ambient pressure paper spray mass spectrometry (PS-MS) was developed. AgNFs were immobilized on nylon-coated paper modified with silver and ethylenediamine. The developed substrate was characterized via scanning electron microscopy and infrared spectroscopy. The densely packed nanoscale petals of the AgNFs lead to a large number of so-called hot spots at their overlapping points, which result in an enhancement of the Raman signal. In addition, the presence of the AgNFs produces an increase in the sensitivity of the mass spectrometric analysis as compared with bare paper and nylon/Ag-coated paper. The dual substrate was evaluated for the identification and quantification of ketoprofen in aqueous standards as well as human saliva from healthy volunteers. The method enables the determination of ketoprofen with a limit of detection and limit of quantification via PS-MS of 0.023 and 0.076 mg L−1, respectively, with a relative standard deviation (RSD) of 3.4% at a concentration of 0.1 mg L−1. This dual substrate enables the simple and fast detection of ketoprofen with minimal sample preparation, providing complementary Raman and mass spectrometric information.

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Acknowledgments

Financial support from the Spanish Ministry of Economy and Competitiveness (CTQ2017-83175R) is gratefully acknowledged. The authors would like to thank Prof. A. Molina, Prof. J.F. García-Reyes and Dr. M. Beneito-Cambra (all of them from the University of Jaen, Spain) for their help with PS-MS technique. Additionally, the authors would like to thank the Central Service for Research Support (SCAI) of the University of Córdoba for the service provided to obtain the micrographs and especially to Carlos Fuentes Almagro, from the Proteomics Units, for all the help with Xcalibur software. This article is based upon work from the Sample Preparation Task Force and Network, supported by the Division of Analytical Chemistry of the European Chemical Society.

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Authors and Affiliations

  1. Departamento de Química Analítica, Instituto Universitario de Investigación en Química Fina y Nanoquímica IUNAN, Universidad de Córdoba, Campus de Rabanales, Edificio Marie Curie, 14071, Córdoba, Spain

    M. C. Díaz-Liñán, M. T. García-Valverde, A. I. López-Lorente, S. Cárdenas & R. Lucena

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  1. M. C. Díaz-Liñán
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  2. M. T. García-Valverde
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  3. A. I. López-Lorente
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  4. S. Cárdenas
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  5. R. Lucena
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Corresponding author

Correspondence to A. I. López-Lorente.

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Informed consent was obtained for saliva samples from all individual participants (healthy volunteers) involved in the study. The study was approved by the appropriate ethics committee (“Comité Ético de Investigación con humanos”) as part of the “Comité de Bioética y Bioseguridad de la Universidad de Córdoba” and was performed in accordance with the ethical standards.

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The authors declare that they have no competing interests.

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Díaz-Liñán, M.C., García-Valverde, M.T., López-Lorente, A.I. et al. Silver nanoflower-coated paper as dual substrate for surface-enhanced Raman spectroscopy and ambient pressure mass spectrometry analysis. Anal Bioanal Chem 412, 3547–3557 (2020). https://doi.org/10.1007/s00216-020-02603-x

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  • DOI: https://doi.org/10.1007/s00216-020-02603-x

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