Abstract

In the last decade, surface-enhanced Raman spectroscopy (SERS) met increasing interest in the detection of chemical and biological agents due to its rapid performance and ultra-sensitive features. Being SERS a combination of Raman spectroscopy and nanotechnology, it includes the advantages of Raman spectroscopy, providing rapid spectra collection, small sample sizes, characteristic spectral fingerprints for specific analytes. In addition, SERS overcomes low sensitivity or fluorescence interference that represents two major drawbacks of traditional Raman spectroscopy. Nanoscale roughened metal surfaces tremendously enhance the weak Raman signal due to electromagnetic field enhancement generated by localized surface plasmon resonances. In this paper, we detected label-free SERS signals for arbitrarily configurations of dimers, trimers, etc., composed of gold nanoshells (AuNSs) and applied to the mapping of osteosarcoma intracellular components. The experimental results combined to a theoretical model computation of SERS signal of specific AuNSs configurations, based on open cavity plasmonics, give the possibility to quantify SERS enhancement for overcoming spectral fluctuations. The results show that the Raman signal is locally enhanced inside the cell by AuNSs uptake and correspondent geometrical configuration generating dimers are able to enhance locally electromagnetic fields. The SERS signals inside such regions permit the unequivocal identification of cancer-specific biochemical components such as hydroxyapatite, phenylalanine, and protein denaturation due to disulfide bonds breaking between cysteine links or proline.

Highlights

  • Raman spectroscopy is a vibrational spectroscopic technique able to identify molecular species in a wide range of analytical applications [1]

  • The enhancement factor is generally composed of two contributions: one is the electric field enhancement factor, Γ(ω) = |E|2 /|E0 |2, where E0 is the incident electric field and E the electric field scattered at the position of the molecule

  • MScs and osteosarcoma cells consists in identifying the major biochemical components characterizing osteosarcoma cells

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Summary

Introduction

Raman spectroscopy is a vibrational spectroscopic technique able to identify molecular species in a wide range of analytical applications [1]. In the last decades, methods for enhancing the signal have been developed in order to enable the detection of small quantities of analytes [2,3,4]. The most efficient method to enhance the Raman signal involves the plasmonic confinement of electromagnetic fields due to metal nanorough surfaces [5]. This method takes the name surface-enhanced Raman spectroscopy (SERS) [6]. The strong Raman signal, generated by the SERS effect, enables short acquisition times consistent with the general requirements for both higher-throughput analysis and biological sampling and imaging [7]. The other one, |Γd |, is the enhancement factor that

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