Chiral Hybrid Nanosystems and Their Biosensing Applications

The presented chapter is devoted to chiral biosensing using various metal nanostructures and their hybrid nanosystems with optically active bio- and organic molecules. Plasmonic nanosystems and nanostructures provide an excellent platform for label-free detection of molecular adsorption by detecting tiny changes in the local refractive index or amplification of light-induced processes in biomolecules. Based on recent theoretical and experimental developments in plasmon-enhanced local electric fields, we consider the main types of molecular-plasmonic hybrid systems capable of generating an amplified chiroptical signal for such applications as detecting the presence of certain biomolecules and (in some cases) determination of their orientation and higher-order structure.

Hybrid Nanosystems Based on Metal-Containing Mesogenic CyanoAlkyl and Alkoxybiphenyls

The paper reviews the results of the authors on the production of hybrid nanosystems based on liquid crystalline (LC) long-chain cyano(alkyl and alkoxy)biphenyls (5CB, 5OCB, and 8CCB) including nanosized metal species. The samples were obtained through the direct incorporation of metal (silver and copper) atoms and small clusters into mesogenic CB matrices via a low temperature co-condensation technique, and the formation of biligand metal complexes were revealed by FTIR and ESR-spectroscopy. The heating of the systems led to the controlled growth of metal clusters and nanosized metal particles of the definite size beginning from 1 up to 200 nanometers, and their highly-ordered assemblies stabilized in the solid and liquid crystalline phases. It is shown that supramolecular ordering in different LC phases of cyanobiphenyl matrices determines the size and shape of nanosized metal species that are formed in the systems under investigation, as well as the morphology of their aggregates. TEM and atomic force microscopy (AFM) data revealed the existence of orientationally-ordered nanostructures in the nematic phases of 5CB and 5OCB. The growth of quasi-fractal 2D-aggregates was shown for layer-structured smectic mesophase of 8CB. The UV–Visible spectra of hybrid metal–mesogenic nanosystems Ag-5CB and Cu-5CB that were incorporated into polymeric films revealed intensive plasmonic bands at 400–450 nm, similar to silver nanoparticles, and 540–650 nm, similar to copper nanoparticles. The increasing of the metal contents in the samples caused the growth of highly anisometric shaped metal rods, with the ratio of the length to the diameter being more than 10 and plasmonic bands at region of λ ≥ 650 nm.