Optical Properties And Surface Enchanced Raman Scattering For Hybrid Nanocomposites Based On Porphyrin Nanotubes And Silver Plasmonic Resonance Particles

Eduard Zenkevich1,  Vladimir Sheinin2,  Sergei Shabunin2,  Elena Bobritskaya3,  Oscar Koifman3,  Natalia Strekal4,  Svetlana Gogoleva4,  Sergei Maskevich4
1National Technical University of Belarus, 220013 Minsk, Belarus, 2G.A. Krestov Institute of Solution Chemistry of RAS, 153045 Ivanovo, Russia, 3Ivanovo State University of Chemistry and Technology, 153000 Ivanovo, Russia, Russia, 4Ya. Kupala Grodno State University, 230023 Grodno, Belarus


Abstract

Recently, it has been shown that porphyrin nanotubes (PNT) are representative of a new class of porphyrin nanostructures for which the molecular building blocks (tectons) can be altered to control their structural and functional properties. Such discrete self-assembled porphyrin nanostructures with well-defined shapes and sizes may be synthesized using a range of methods including ionic self-assembly, reprecipitation, and coordination polymerization. In this report, we are willing to describe physico-chemical backgrounds for the governed formation of porphyrin j-aggregates (j-AP) and porphyrin nanotubes (PNT) in solutions and on colloid resonance plasmon Ag particles (RPP) fixed on a quartz surface as well as to discuss their optical properties and surface enhanced Raman spectra (SERS). Water-soluble zwitterion H4P2+(PhSO3)4 was used as a basic precursor for the formation of porphyrin j-aggregates (j-AP) which in their turn are capable to the pH-induced formation of self-assembled PNTs of various structure. AFM investigations of j-AP films have shown the formation of non-uniform islands with a height in the order of 10 to several 10 nanometers. Based on the analysis of AFM spectra profiles it has been evaluated that zwitterion molecules assemble into irregular globular shapes of different sizes around several 10 nanometers which are arranged in an non-ordered fashion on the surface. The RMS roughness is about 7-10 nm for aggregates and film thickness has been estimated to be around 25 nm. Experimental SERS spectra have been obtained for zwitterion (precursor) adsorbed on colloid resonance plasmon Ag particles (RPP) with sizes of 10-15 nm as well as quantum-chemical calculations (FireFly 8.0.1) of the structure and vibrational spectra have been carried out. Based on a comparative analysis of intensities and frequencies of vibration bands in calculated Raman and measured SERS spectra two possible geometries for zwitterion adsorption on RPP surface have been proposed leading to the twist of the zwitterion plane. The porphyrin nanotubes formed by ionic self-assembly of two porphyrins with opposite charge are of particular interest because their hollow tubular structure lends itself to the construction of nanotube-metal composites of various architectures. In this case, SERS became a a very useful tool for the detection and recognition of supramolecular species at very low concentration. In this respect, we have succeeded to fix PNTs on nanoplasmonic structures that is on colloid resonance plasmon Ag particles (RPP) with sizes of 10-15 nm. RPP present a disordered nanotextured silver surface in which surface plasmon resonance and/or localized plasmons can be excited under resonance conditions. Such structures are widely used for the enhancement of both Raman scattering and fluorescence. We have shown that the formation of SERS spectra for PNT fixed on colloid resonance plasmon Ag particles are cased by surface plasmon resonances and localized plasmons. To the best of our knowledge the corresponding data for plasmonic effects in metallo-organic hybrid nanocomposites of “PNT+RPP” type are absent in literature. The presented results show new perspectives in the field of organic-nonorganic supramolecular chemistry toward the formation of “tailored”species including porphyrin nanotubes possessing unique physico-chemical properties.