Noble Metal Nanoparticles Prepared by Metal Sputtering into Glycerol and their Grafting to Polymer Surface

This chapter summarizes the basic information about elementary characteristics and technology of preparation of noble metal nanoparticles. The introduction gives some basic information on the history of development in this area, especially in terms of dimensionality of metal nanostructures and their possible applications.The first subsection is devoted to the preparation and characterization of Au, Ag, Pt, and Pd nanoparticles (NPs), which were synthesized by direct metal sputtering in liquid propane-1,2,3,-triole (glycerol). This method provides an interesting alternative to time-consuming, wet-based chemical synthesis techniques. Moreover, the suggested technique allows targeted variation of metal nanoparticle size, which is demonstrated in detail in case of AuNPs by variation of capturing media temperature. Nanoparticle size and shape were studied by transmission electron microscopy and dynamic light scattering. Optical properties of nanoparticle solution were determined by measuring its UV–Vis spectra. Concentration of metal nanoparticles in prepared solutions was determined by atomic absorption spectroscopy. Antibacterial properties were tested against two common pollutants (Escherichia coli, a Gram-negative bacteria, and Staphylococcus epidermidis, a Gram-positive bacteria). In the presence of Ag nanoparticles, the growth of E. coli and S. epidermidis was completely inhibited after 24 h. Any growth inhibition of E. coli was observed neither in the presence of “smaller” (4–6 nm, AuNP4–6) nor “bigger” (9–12 nm, AuNP8–12) AuNPs during the whole examination period. AuNP4–6, but not AuNP8–12, was able to inhibit the growth of. S epidermidis. We also observed significant difference in biological activities of Pt and PdNPs. More specifically, PdNPs exhibited considerable inhibitory potential against both E. coli and S. epidermidis, which was in contrast to ineffective PtNPs. Our results indicate that Ag, Pd, and partially AuNPs have high potential to combat both Gram-positive and Gram-negative bacterial strains.The second subsection describes the effort to anchor metal nanoparticles onto polyethyleneterephthalate (PET) carrier. Two different procedures of grafting of polymeric carrier, activated by plasma treatment, with Au and AgNPs are described. In the first procedure, the PET foil was grafted with biphenyl-4,4’-dithiol (BPD) and subsequently with Au and AgNPs. In the second one, the PET foil was grafted with Au and AgNPs previously coated by the same BPD. X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and electrokinetic analysis were used for characterization of the polymer surface at different modification steps. Au and AgNPs were characterized by UV–Vis spectroscopy. In case of both types of nanoparticles, the first procedure was found to be more effective. It was proved that the BPD was chemically bonded to the surface of the plasma-activated PET and it mediates subsequent grafting of the AuNPs

Properties of gold nanostructures sputtered on glass

We studied the electrical and optical properties, density, and crystalline structure of Au nanostructures prepared by direct current sputtering on glass. We measured temperature dependence of sheet resistance and current-voltage characteristics and also performed scanning electron microscopy [SEM] analysis of gold nanolayers. It was shown that within the wide range of temperatures, gold nanolayers (<10 nm) exhibit both metal and semiconducting-like type of conductivity. UV/Vis analysis proved the semiconducting characteristic of intrinsic Au clusters. SEM analysis showed the initiatory stadium of gold layer formation to be running over isolated islands. Gold density calculated from the weight and effective thickness of the layers is an increasing function of the layer thickness up to approximately 100 nm. In thin layers deposited on solid surface, a lattice expansion is observed, which is manifested in the increase of the lattice parameter and the decrease of metal density. With increasing layer thickness, the lattice parameter and the density approach the bulk values

Annealing of gold nanostructures sputtered on polytetrafluoroethylene

Gold nanolayers sputtered on polytetrafluoroethylene (PTFE) surface and their changes induced by post-deposition annealing at 100°C to 300°C are studied. Changes in surface morphology and roughness are examined by atomic force microscopy, electrical sheet resistance by two point technique, zeta potential by electrokinetic analysis and chemical composition by X-ray photoelectron spectroscopy (XPS) in dependence on the gold layer thickness. Transition from discontinuous to continuous gold coverage takes place at the layer thicknesses 10 to 15 nm and this threshold remains practically unchanged after the annealing at the temperatures below 200°C. The annealing at 300°C, however, leads to significant rearrangement of the gold layer and the transition threshold increases to 70 nm. Significant carbon contamination and the presence of oxidized structures on gold-coated samples are observed in XPS spectra. Gold coating leads to a decrease in the sample surface roughness. Annealing at 300°C of pristine PTFE and gold-coated PTFE results in significant increase of the sample surface roughness

Structure-Dependent Biological Response of Noble Metals: From Nanoparticles, Through Nanowires to Nanolayers

Noble metals in their diverse nanoforms bring revolution to many fields of science and technology, as they provide unique properties over their bulk counterparts. Thanks to these completely unprecedented properties, commercial sphere pressure is growing to use them in everyday life. Unfortunately, one of the issues that are subject to dramatic changes is the reactivity of these structures. This may have often fatal consequences to the living organisms. Due to the fact that the mechanism of action of metal nanostructures on living organisms is not yet fully elucidated even in the case of the most studied noble metals such as gold and silver, it is necessary to continue intensively in their research, characterization and categorization. The main prerequisite for the undistorted study of interactions of nanostructures with living organisms is the use of suitable methods of their preparation. Within this context, this chapter attempts to summarize current knowledge form the field of synthesis of metal nanoparticles, layers, wires, and other nanostructures, especially regarding novel techniques of their preparation and extend them by our own results in this area, in the context of their biological properties. More specifically, antibacterial efficacy and potential cytotoxicity of those structures are thoroughly addressed

Polytetrafluorethylene-Au as a substrate for surface-enhanced Raman spectroscopy

This study deals with preparation of substrates suitable for surface-enhanced Raman spectroscopy (SERS) applications by sputtering deposition of gold layer on the polytetrafluorethylene (PTFE) foil. Time of sputtering was investigated with respect to the surface properties. The ability of PTFE-Au substrates to enhance Raman signals was investigated by immobilization of biphenyl-4,4'-dithiol (BFD) from the solutions with various concentrations. BFD was also used for preparation of sandwich structures with Au or Ag nanoparticles by two different procedures. Results showed that PTFE can be used for fabrication of SERS active substrate with easy handle properties at low cost. This substrate was sufficient for the measurement of SERS spectrum of BFD even at 10-8 mol/l concentration

Noble Metal Nanostructures Influence of Structure and Environment on Their Optical Properties

Optical properties of nanostructured materials, isolated nanoparticles, and structures composed of both metals and semiconductors are broadly discussed. Fundamentals of the origin of surface plasmons as well as the surface plasmon resonance sensing are described and documented on a number of examples. Localized plasmon sensing and surface-enhanced Raman spectroscopy are subjected to special interest since those techniques are inherently associated with the direct application of plasmonic structures. The possibility of tailoring the optical properties of ultra-thin metal layers via controlling their shape and morphology by postdeposition annealing is documented. Special attention is paid to the contribution of bimetallic particles and layers as well as metal structures encapsulated in semiconductors and dielectrics to the optical response. The opportunity to tune the properties of materials over a large scale of values opens up entirely new application possibilities of optical active structures. The nature of surface plasmons predetermines noble metal nanostructures to be promising great materials for development of modern label-free sensing methods based on plasmon resonance—SPR and LSPR sensing

"Soft and rigid" dithiols and Au nanoparticles grafting on plasma-treated polyethyleneterephthalate

Surface of polyethyleneterephthalate (PET) was modified by plasma discharge and subsequently grafted with dithiols (1, 2-ethanedithiol (ED) or 4, 4'-biphenyldithiol) to create the thiol (-SH) groups on polymer surface. This "short" dithiols are expected to be fixed via one of -SH groups to radicals created by the plasma treatment on the PET surface. "Free" -SH groups are allowed to interact with Au nanoparticles. X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and electrokinetic analysis (EA, zeta potential) were used for the characterization of surface chemistry of the modified PET. Surface morphology and roughness of the modified PET were studied by atomic force microscopy (AFM). The results from XPS, FTIR, EA and AFM show that the Au nanoparticles are grafted on the modified surface only in the case of biphenyldithiol pretreatment. The possible explanation is that the "flexible" molecule of ethanedithiol is bounded to the activated PET surface with both -SH groups. On the contrary, the "rigid" molecule of biphenyldithiol is bounded via only one -SH group to the modified PET surface and the second one remains "free" for the consecutive chemical reaction with Au nanoparticle. The gold nanoparticles are distributed relatively homogenously over the polymer surface