Multiplex micro-SERS imaging of cancer-related markers in cells and tissues using poly(allylamine)-coated Au@Ag nanoprob
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Multiplex micro-SERS imaging of cancer-related markers in cells and tissues using poly(allylamine)-coated Au@Ag nanoprobes Alexandre Verdin 1 & Cedric Malherbe 1 & Wendy Heukemes Müller 1 & Virginie Bertrand 1 & Gauthier Eppe 1 Received: 11 June 2020 / Revised: 5 August 2020 / Accepted: 28 August 2020 # Springer-Verlag GmbH Germany, part of Springer Nature 2020
Abstract Surface-enhanced Raman scattering (SERS) nanoprobes based on Au@Ag core@shell nanoparticles coated with poly(allylamine) were functionalized with small targeting molecules to evaluate simultaneously the level of expression of two cancer-related markers, both in cells and in tissues. The Au@Ag nanoparticles provide a high SERS signal enhancement in the visible range when combined with resonant Raman-active molecules. The poly(allylamine) coating plays a dual key role in (i) protecting the metal surface against the complex biological medium, leading to a stable signal of the Raman-active molecules, and (ii) enabling specific biofunctionalization through its amine functions. Using small targeting molecules linked to the polymer coating, two different nanoprobes (duplex approach) were designed. Each was able to specifically target a particular cancerrelated marker: folate receptors (FRs) and sialic acid (SA). We demonstrate that the level of expression of these targeted markers can be evaluated following the SERS signal of the probes incubated on cells or tissues. The potential overexpression of folate receptors and of sialic acid was evaluated and measured in breast and ovarian cancerous tissue sections. In addition, FR and/or SA overexpression in the tumor region can be visualized with high contrast with respect to the healthy region and with high spatial accuracy consistent with histology by SERS imaging of the nanoprobe signal. Owing to the unique spectral signature of the designed nanoprobes, this approach offers an efficient tool for the spatially resolved, in situ measurement of the expression level of several cancer-related markers in tumors at the same time. Keywords Nanoparticles . Molecular imaging . Cancer . Raman . Micro-SERS . Multiplex
Introduction Raman spectroscopy imaging (RSI) is increasingly used to visualize the molecular distribution of numerous classes of biomolecules in tissue sections at high spatial resolution [1, 2]. However, Raman spectra of biological samples generally include bands that are common to general classes of molecules (DNA, proteins, lipids, etc.) and often highly overlapping. Therefore, the specific detection-identification of a particular molecule of interest in a biological sample from its Raman spectrum is not straightforward. In addition, Raman cross Electronic supplementary material The online version of this article (https://doi.org/10.1007/s00216-020-02927-8) contains supplementary material, which is available to authorized users. * Gauthier Eppe [email protected] 1
Mass Spectrometry Laboratory, MolSys Research Unit, University of Liège, 4000 Liège, Belgium
sections of organic molec
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