Surface enhanced Raman spectroscopy (SERS) represents a promising technique in providing specific molecular information that could have a major impact in biomedical applications, such as early cancer detection. SERS requires the presence of a suitable plasmonic substrate that can generate enhanced and reproducible diagnostic relevant spectra. In this paper, we propose a new approach for the synthesis of such a substrate, by using concentrated silver nanoparticles purified using the Tangential Flow Filtration method. The capacity of our substrates to generate reproducible and enhanced Raman signals, in a manner that can allow cancer detection by means of Multivariate Analysis (MVA) of Surface Enhanced Raman (SER) spectra, has been tested on blood plasma samples collected from 35 healthy donors and 29 breast cancer patients. All the spectra were analyzed by a combined Principal Component-Linear Discriminant Analysis. Our results facilitated the discrimination between healthy donors and breast cancer patients with 90% sensitivity, 89% specificity and 89% accuracy. This is a direct consequence of substrates’ ability to generate diagnostic relevant spectral information by performing SERS measurements on pristine blood plasma samples. Our results suggest that this type of solid substrate could be employed for the detection of other types of cancer or other diseases by means of MVA-SERS procedure.

Biological effects of low-dose ionizing radiation (IR) have been unclear until now. Saliva, because of the ease of collection, could be valuable in studying low-dose IR effects by means of surface-enhanced Raman spectroscopy (SERS). The objective of our study was to compare the salivary SER spectra recorded before and after low-dose IR exposure in the case of pediatric patients (PP). Unstimulated saliva was collected from ten PP before and after irradiation with a cone beam computed tomography (CBCT) machine used for diagnostic purposes. The SERS measurements have been recorded on dried saliva samples using a solid nanosilver plasmonic substrate synthesized using an original method developed in our laboratory. The experimental results showed that salivary SER spectra are dominated by three vibrational bands (441,735 and 2107 cm−1) that can be assigned to bending and stretching vibrations of salivary thiocyanate (SCN-). After exposure, an immediate increase of vibrational bands assigned to SCN- has been recorded in the case of all samples, probably as a result of IR interaction with oral cavity. This finding suggests that SCN- could be used as a valuable biomarker for the detection and identification of low-dose radiation effects.

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In this letter, we report a new, one-step, rapid, and easy-to-implement method for the synthesis of PEGylated gold nanoparticles (PEG-AuNPs) having a narrow size distribution and very interesting plasmonic properties. Unmodified polyethylene glycol molecules with a molecular weight of 1000 g/mole (PEG1000) have been employed as reducing and capping agents for the synthesis of spherical gold nanoparticles having an average diameter of 35 nm, within a few minutes. The novelty of the herein proposed synthesis method consists in the fact that the synthesis takes place inside of a sealed bottle flask containing aqueous solutions of PEG1000, tetrachloroauric(III) acid (HAuCl4), and NaOH, placed in the center of a microwave oven, capable to provide a very uniform temperature environment. It turned out that, during the very short synthesis procedure (2 minutes), PEG 1000 suffers an oxidative transformation in such a manner that its terminal alcohol groups (-CH2-OH) are transformed in carboxylate ones (-COO−). The as-synthesized PEG-AuNPs possess very interesting plasmonic properties allowing the detection of different molecules by means of SER spectroscopy performed either in liquid droplets or on solid spots. As a consequence of their unique plasmonic properties, the SER spectra acquired using this new class of nanoparticles on different molecules of interest (methylene blue, rhodamine 6G, doxorubicin, and 5-fluorouracil) are highly reproducible, making them ideal candidates for further use as SERS substrates.

It is possible to obtain diagnostically relevant data on the changes in biochemical elements brought on by cancer via the use of multivariate analysis of vibrational spectra recorded on biological fluids. Prostate cancer and control groups included in this research generated almost similar SERS spectra, which means that the values of peak intensities present in SERS spectra can only give unspecific and limited information for distinguishing between the two groups. Our diagnostic algorithm for prostate cancer (PCa) differentiation was built using principal component analysis and linear discriminant analysis (PCA-LDA) analysis of spectral data, which has been widely used in spectral data management in many studies and has shown promising results so far. In order to fully utilize the entire SERS spectrum and automatically determine the most meaningful spectral features that can be used to differentiate PCa from healthy patients, we perform a multivariate analysis on both the entire and specific spectral intervals. Using the PCA-LDA model, the prostate cancer and control groups are clearly distinguished in our investigation. The separability of the following two data sets is also evaluated using two alternative discrimination techniques: principal least squares discriminant analysis (PLS-DA) and principal component analysis—support vector machine (PCA-SVM).

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Chiral separation is an important issue for the pharmaceutical industry. Over the years, several separation methods have been developed, mainly based on chromatography. Their working principle is based on the formation of transient diastereoisomers, but the very subtle nanoscale interactions responsible for separation are not always understood. Recently, Raman and surface-enhanced Raman (SERS) spectroscopy have provided promising results in this field. Here we present Raman/SERS experimental data that provide useful information concerning the nanoscale interactions between propranolol enantiomers and α, β, and γ cyclodextrins. Raman spectroscopy was used to prove the formation of host–guest intermolecular complexes having different geometries of interaction. The occurrence of new vibrational bands and a change in the intensities of others are direct proofs of complexes’ formation. These observations were confirmed by DFT calculations. By performing SERS measurements on a new type of plasmonic substrate, we were able to prove the intermolecular interactions responsible for PRNL discrimination. It turned out that the interaction strength between the substrate and the intermolecular complexes is of paramount importance for SERS-based chiral discrimination. This approach could represent a very good starting point for the evaluation of molecular interactions manifesting between other pharmaceutical compounds and different classes of chiral selectors.