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The review concerns the state of the art, the advances in and prospects for application of surface-enhanced Raman spectroscopy (SERS) in chemical analysis. Key advantages (nondestructive origin, high sensitivity and selectivity, easiness of sample preparation) and drawbacks (a relatively small number of analytes, insufficient metrological characteristics of certain objects) of the method are pointed out. Particular attention is paid to the development of novel chemical approaches and to the design of versatile optical sensors to significantly enhance the analytical potential of the method and to extend the range of analytes. Examples are given of the application of SERS in key branches of science and technology that require both qualitative and quantitative chemical analysis of complex objects, viz., environmental monitoring, fuel and energy area, medical diagnosis, biology and biochemistry. The bibliography includes 502 references.

This communication suggests a new approach expanding the range of important analytes becoming available for Raman scattering enhancement due to entrapping them into charge-transfer complexes immobilized onto nanostructured substrates.

A novel concept of advanced SERS (surface enhanced Raman spectroscopy) planar sensors is suggested for fast analysis of sulfur-containing hazardous oil components and persistent pollutants. The main advantage of the proposed sensors is the utilization of an additional preconcentrating layer of optically transparent chitosan gel, which is chemically modified with appropriate π-acceptor compounds to selectively form charge-transfer complexes (CTCs) at the interface with nanostructured silver coatings. The CTCs shift absorption bands of polycyclic aromatic sulfur heterocycles (PASHs) and other important analytes in a controllable way and thus provide a surplus enhancement of vibration modes due to resonant Raman scattering. This novel indicator system provides multiplex determination of PASHs in different forms in a small volume of oil without any tedious sample pretreatment steps. This approach opens new possibilities of increasing either spectral and concentration sensitivity or specificity of SERS-based sensors, allowing for new developments in the fields of ecology, advanced fuel analysis, and other prospective applications.

Herein, a silver-chitosan nanocomposite for application in surface enhanced Raman spectroscopy (SERS) sensing was proposed. It was shown that optically transparent chitosan coatings with 0.8 μm thickness allow penetration of target analytes to silver nanoparticles and the analysis in both polar and nonpolar solvents. Under the chosen conditions, chitosan formed continuously smooth films and coatings stabilizing rough nanostructured metallic surfaces and served as a suitable matrix for immobilization, uniform spreading, and preconcentration of the analytes. Polycyclic aromatic sulfur heterocycles were chosen as target analytes being one of the most important fuel quality markers, hazardous components, and the hardest-to-remove impurities. For the most effective immobilization and even distribution of the analytes onto a nanostructured metallic surface, an additional polymer layer of chitosan was found to be needed. The presence of thin films of chitosan resulted in higher reproducibility of SERS spectra as compared to bare nanostructured silver substrates. Additionally, the developed nanocomposite SERS sensors provided the rapid determination of dibenzothiophene and its derivatives in isooctane with the threshold of detection better than 0.1 μM. This approach was successfully applied in the analysis of real fuel samples and the results agreed well with independently measured FTIR and GC-MS data.