Search

A new generation of reconfigurable optical components is conceived by bridging the photothermal properties of gold nanoparticles and the thermosensitivity of liquid crystalline materials. As such, gold nanorods (GNRs) heated using light are used to activate efficient hidden diffraction gratings realized in a blend made of a room temperature polymerizable liquid crystal (PLC) and nematic liquid crystal (NLC). Holographic liquid crystal polymer dispersed liquid crystal (HLCPDLC) gratings containing a small percentage of GNRs are fabricated with periodicity of 2.6 ?m by means of a conventional UV holographic recording setup. The HLCPDLC structures are characterized using morphological, optical, and thermooptical techniques. Because of the initial refractive index match between the polymer-rich and LC-rich regions, the "grating" is hidden and the films appear transparent and nondiffractive. Illumination of these GNR-containing structures with a suitable light source (808 nm) induces a local heating due to the plasmonic absorption of the GNRs. This heating induces a refractive index mismatch between the PLC and the NLC as the latter undergoes a phase transition from nematic to isotropic, finally resulting in a transmission diffractive structure activated over a few seconds exhibiting an efficiency of about 70%. The same HLCPDLC samples have also been tested as thermosensitive waveplates, enabling a new, fast methodology for quantifying the photoinduced plasmonic heating with a thermal sensitivity of ?0.04 °C. Moreover, thermoplasmonic driven waveplates represent a new avenue in the field of light controllable optical phase modulators.

Photo-oxidation processes assisted by nanosized semiconductors are receiving increasing attention due to their potential application in environmental field. The ability to exploit the strong potential of photoactive nanomaterials and access their properties relies on the ability to integrate them in photo-reactors and to effectively deposit them on large surfaces. Such a strategy can bridge the gap between the nanoscopic and mesoscopic scale and avoiding nanoparticle release in the environment. In order to integrate nanopartides in functional structures and, finally, devices, their incorporation in suitable host matrices is crucial to achieve processable nanocomposite materials. Here, a comprehensive overview on the preparation of photocatalytic nanocomposite materials and their application for pollutants degradation will be provided. In particular, we will focus on modern synthetic approaches to synthetize UV and visible light active nanocatalysts, on their post-synthesis surface functionalization and on their incorporation in suitable host matrices toward nanocomposite preparation. Finally, some examples from recent literature on their application in environmental remediation and as bactericidal and self-cleaning coatings will be reported. (C) 2016 Elsevier B.V. All rights reserved.

Plasmonic photo-thermal therapy (PPTT) is a minimally invasive, drug-free, therapy based on the properties of noble metal nanoparticles, able to convert a bio-transparent electromagnetic radiation into heat. PPTT has been used against cancer and other diseases. Herein, we demonstrate an antimicrobial methodology based on the properties of gold nanorods (GNRs). Under a resonant laser irradiation GNRs become highly efficient light to heat nano-converters extremely useful for PPTT applications. The concept here is to assess the antimicrobial effect of easy to synthesize, suitably purified, water-dispersible GNRs on Escherichia coli bacteria. A control on the GNRs concentration used for the process has been demonstrated critical in order to rule out cytotoxic effects on the cells, and still to be able to generate, under a near infrared illumination, an adequate amount of heat suited to increase the temperature up to &asymp, 50 &deg, C in about 5 min. Viability experiments evidenced that the proposed system accomplished a killing efficiency suitable to reducing the Escherichia coli population of about 2 log CFU (colony-forming unit).

Plasmonic photo-thermal therapy (PPTT) is a minimally invasive, drug-free, therapy based on the properties of noble metal nanoparticles, able to convert a bio-transparent electromagnetic radiation into heat. PPTT has been used against cancer and other diseases. Herein, we demonstrate an antimicrobial methodology based on the properties of gold nanorods (GNRs). Under a resonant laser irradiation GNRs become highly efficient light to heat nano-converters extremely useful for PPTT applications. The concept here is to assess the antimicrobial effect of easy to synthesize, suitably purified, water-dispersible GNRs on Escherichia coli bacteria. A control on the GNRs concentration used for the process has been demonstrated critical in order to rule out cytotoxic effects on the cells, and still to be able to generate, under a near infrared illumination, an adequate amount of heat suited to increase the temperature up to ≈50 °C in about 5 min. Viability experiments evidenced that the proposed system accomplished a killing efficiency suitable to reducing the Escherichia coli population of about 2 log CFU (colony-forming unit).

Thermo-sensitive liquid crystals may result, for some aspects, good host materials for plasmonic nanoparticles. In particular they are suitable to study and measure the temperature variations produced by photo-induced plasmonic joule effect in the metallic nanoparticles. Combining the properties of liquid crystals and metallic nanoparticles, allows to measure temperature variations in different ways by exploiting the optical properties of thermotropic liquid crystals: In a first attempt, by combining nematic liquid crystals and spherical metallic nanoparticles, we have predicted and measured temperature changes, under a suitable (resonant) optical illumination, by measuring the photo-thermal induced birefringence variation. In a different experiment, we have combined cholesteric liquid crystals and gold nanorods: Light-induced variations of structural colorations exhibited by cholesteric liquid crystals has been used as a new methodology to measure nanoscale heat variation with a very high sensitivity (0.03 K).

The stability of Chlorophyll a in water during prolonged exposure, at room temperature, to a neon lamp has been investigated by means of UV-vis and fluorescence spectroscopies. In addition, the Chlorophyll a (photo)stability evaluation in presence of suitable carriers has been performed in order to investigate its reactivity under the same conditions, for possible and future applications in Antimicrobial Photodynamic Therapy. Cetyltrimethylammonium chloride was chosen to solubilize Chlorophyll a in water. While, cetyltrimethylammonium chloride-capped gold nanoparticles offer a great opportunity because combine the Chlorophyll a action, used as a photosensitizer in Antimicrobial Photodynamic Therapy, with gold nanoparticles effect used in photothermal therapy. Indeed, the latter ones have exhibited an interesting rise of temperature if irradiated with visible light. Overall, both examined systems, cetyltrimethylammonium chloride/Chlorophyll a and gold nanoparticles/Chlorophyll a, were able to induce the Reactive Oxygen Species formation fundamental for a potential application in Antimicrobial Photodynamic Therapy. (C) 2017 Elsevier B.V. All rights reserved.

Au nanorods (NRs) modified nanostructured TiO2/ITO electrodes have been fabricated and characterized in order to develop a biosensing platform for the photoelectrochemical determination of microRNAs. The proposed method is based on the use of thiolated DNA capture-probes (CPs) immobilized onto Au NR surface. The Au NRs are chemically bound at the surface of TiO2/ITO electrodes by means of the mercaptosuccinic acid linker. Subsequently, the DNA CPs are bound to the Au NR surface through the thiolate group, and reacted with the target RNA sequence. Finally, the obtained biosensing platform is incubated with alkaline phosphatase and I.-ascorbic acid 2-phosphate (AAP) enzymatic substrate, for the in situ generation of ascorbic acid (AA). Such AA molecule, coordinating to surface Ti atoms, generates a charge transfer complex, that results in a shift of the UV absorption threshold toward the visible spectral region of the nanostructured TiO2 forming the electrode and, hence, in the occurrence of an absorption band centered at 450 nm. The photoelectrochemical monitoring of the formation of the AA-TiO2 complex, under the visible light of a commercial LED light source, allows the selective and quantitative detection of the target microRNA strands. (C) 2018 Elsevier Ltd. All rights reserved.

Localized plasmon resonance (LPR) of noble Metal Nanoparticles (MNPs) opens up a new horizon for nanoscale materials able to convert light into heat, since the strong electric field generated around the MNPs can transform them into original heat nanosources. Thus, investigation of the heat transport mechanism, from the heated MNPs to their surrounding medium, is fundamental for realizing applications in nanotechnology and thermal-based therapies, and a challenge is definitely represented by the possibility of measuring temperature variations at the surface of the MNPs undergoing optical illumination. In this framework, we show that an ingenious combination of characteristics of short pitch liquid crystalline compounds and MNPs has demonstrated effective to provide an advanced tool to monitor nanoscale temperature variations.

The innovative photoelectrochemical properties of multifunctional nanomaterials are here investigated for the development of biosensing platforms for rapid and sensitive detection of a class of cancer biomarker candidates, known as microRNAs. Many different transducers have been proposed, so far, for microRNA detection. Recently, with the emergence of novel photoelectrochemically active species and new detection schemes, photoelectrochemistry has received increasing attention. Gold nanostructures have been, here, used to modify TiO2 electrodes. The surface of the nanostructured platform has been modified by nucleic acid capture probes (CPs). Biotinylated target miRNAs have been recognized by the specific CPs. The biosensing platform has been incubated with streptavidin alkaline phosphatase and exposed to a proper substrate. The product of the enzymatic reaction has been photoelectrochemically monitored. A compact and hand-held analytical device has been developed in order to have a final prototype in line with the concept of point of care testing. (C) 2017 The Authors. Published by Elsevier Ltd.

We have investigated and characterized the unique properties of a liquid crystalline DNA in terms of template and spontaneous-assisted organization by exploiting both top-down and bottom-up approaches. The chemical and physical properties of a passive polymeric template are used to assist the long-range order of a long and short DNA, trapped within microperiodic channels (top-down approach). The spontaneous self-organization of a human genomic DNA is used, by means of an electrostatic mechanism, to organize gold nanorods at the nanoscale (bottom-up approach). The main opportunity highlighted in our studies is the extraordinary capability to realize several applications ranging from photonics to plasmonics by exploiting the intrinsic properties of a bio-inspired material.

We report on photo-thermal effects observed in gold nanoparticles (GNPs) dispersed in Nematic Liquid Crystals (NLCs). Under a suitable optical radiation, GNPs exhibit a strong light absorption/scattering; the effect depends on the refractive index of the medium surrounding the nanoparticles, which can be electrically or optically tuned. In this way, the system represents an ideal nano-source of heat, remotely controllable by light to adjust the temperature at the nanoscale. Photo-induced temperature variations in GNPs dispersed in NLCs have been investigated by implementing a theoretical model based on the thermal heating equation applied to an anisotropic medium; theoretical predictions have been compared with results of experiments carried out in a NLC medium hosting GNPs. Both theory and experiments represent a step forward to understand the physics of heat production at the nanoscale, with applications that range from photonics to nanomedicine.

We report on the thermo-optical properties of gold nanorods (GNRs) dispersed in a thermotropic cholesteric liquid crystal (CLC). We have characterized the CLC reflection band behavior for two different cell thicknesses under the influence of a suitable (resonant) pump beam. It turns out that for the 1.6 mu m thick cell there is a suppression of the CLC reflection band for both pure CLC and CLC/GNRs. For the 10 mu m thick cell, the presence of GNRs desensitizes the shift of the CLC reflection band to temperature. Suitable cell design enables one to 'turn off' the wavelength shift of the peak reflection, thereby turning the system into a pure amplitude measurement tool. This has implications where the probe wavelength is fixed at a common, single wavelength.

Novel photosensitizing film based on the natural hybrid polymer Chitosan/2-hydroxy-propyl-b-Cyclodextrin (CH/CD) is synthesized introducing Chlorophyll a (CH/CD/Chla) as a photoactive agent for possible application in antimicrobial photodynamic therapy (PDT). The polymer absorbs visible light, in turn able to generate reactive oxygen species (ROS) and, therefore it can be used as environmental friendly and biodegradable polymeric photosensitizer (PS). The modified film is characterized by means of different spectroscopic, calorimetric, diffraction techniques and microscopic imaging methods including time-resolved absorption spectroscopy. UVeVis, FTIR-ATR and X-ray Photoelectron Spectroscopy (XPS) analyses suggest that Chla shows a strong affinity toward Chitosan introducing interactions with amino groups present on the polymer chains. Nanosecond laser flash photolysis technique provides evidence for the population of the excited triplet state of Chla. Photogeneration of singlet oxygen is demonstrated by both direct detection by using infrared luminescence spectroscopy and chemical methods based on the use of suitable traps. Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM) and Differential Scanning Calorimetry (DSC) analyses confirm also the occurrence of structural changes both on the film surface and within the film layer induced by the insertion of the pigment. Moreover, X-ray Diffraction data (XRD) shows the existence of an amorphous phase for the chitosan films in all the compared conditions.

Novel photosensitizing film based on the natural hybrid polymer Chitosan/2-hydroxy-propyl-β-Cyclodextrin (CH/CD) is synthesized introducing Chlorophyll a (CH/CD/Chla) as a photoactive agent for possible application in antimicrobial photodynamic therapy (PDT). The polymer absorbs visible light, in turn able to generate reactive oxygen species (ROS) and, therefore it can be used as environmental friendly and biodegradable polymeric photosensitizer (PS). The modified film is characterized by means of different spectroscopic, calorimetric, diffraction techniques and microscopic imaging methods including time-resolved absorption spectroscopy. UV–Vis, FTIR-ATR and X-ray Photoelectron Spectroscopy (XPS) analyses suggest that Chla shows a strong affinity toward Chitosan introducing interactions with amino groups present on the polymer chains. Nanosecond laser flash photolysis technique provides evidence for the population of the excited triplet state of Chla. Photogeneration of singlet oxygen is demonstrated by both direct detection by using infrared luminescence spectroscopy and chemical methods based on the use of suitable traps. Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM) and Differential Scanning Calorimetry (DSC) analyses confirm also the occurrence of structural changes both on the film surface and within the film layer induced by the insertion of the pigment. Moreover, X-ray Diffraction data (XRD) shows the existence of an amorphous phase for the chitosan films in all the compared conditions.

In this study, ultrathin film multilayers of Photosystem II-enriched photosynthetic membranes (BBY) were prepared and immobilized on quartz substrates by means of a Layer by Layer procedure exploiting electrostatic interactions with poly(ethylenimine) as polyelectrolyte. The biomaterials thus obtained were characterized by means of optical techniques and Atomic Force Microscopy, highlighting the fact that the Layer by Layer approach allowed the BBYs to be immobilized with satisfactory results. The activity of these hybrid materials was evaluated by means of optical assays based on the Hill Reaction, indicating that the biosamples, which preserved about 65% of their original activity even ten weeks after preparation, were both stable and active. Furthermore, an investigation of the biochips’ sensitivity to the herbicide terbutryn, as a model analyte, gave interesting results: inhibition of photosynthetic activity was observed at terbutryn concentrations higher than 10−7 M, thus evidencing the potential of such biomaterials in the environmental biosensor field.

An ingenious combination of plasmonic nanomaterials and one of the most relevant biological systems, deoxyribonucleic acid (DNA) is achieved by bioconjugating gold nanorods (GNRs) with DNA via electrostatic interaction between positively charged GNRs and negatively charged short DNA. The obtained system is investigated as a function of DNA concentration by means of gel electrophoresis, zeta-potential, DNA melting and morphological analysis. It turns out that the obtained bioconjugated systems present both effective electric charge and aggregate size that are particularly amenable for gene therapy and nanomedicine applications. Finally, the effect of the localized (photo-thermal heating) and delocalized temperature variation on the DNA melting by performing both light induced bio-transparent optical heating experiments and a thermographic analysis is investigated, demonstrating that the developed system can be exploited for monitoring nanoscale temperature variation under optical illumination with very high sensitivity.

The last few years have seen a growing interest in the ability of metallic nanoparticles (MNPs) to control temperature at the nanoscale. Under a suitable optical radiation, MNPs feature an enhanced light absorption/scattering, thus turning into an ideal nano-source of heat, remotely controllable by means of light. In this framework, we report our recent efforts on modeling and characterizing the photo-thermal effects observed in gold nanoparticles (GNPs) dispersed in thermotropic Liquid Crystals (LCs). Photo-induced temperature variations in GNPs dispersed in Nematic LCs (NLCs) have been studied by implementing an ad hoc theoretical model based on the thermal heating equation applied to an anisotropic medium. Theoretical predictions have been verified by performing photo-heating experiments on a sample containing a small percentage of GNPs dispersed in NLCs. Both theory and experiments represent an important achievement in understanding the physics of heat transfer at the nanoscale, with applications ranging from photonics to nanomedicine.

When light interacts with plasmonic nanoparticles, their free electrons are driven by the alternating electric field and collectively oscillate at a resonant frequency leading to a phenomenon known as surface plasmon resonance. The frequency and amplitude of the resonance are sensitive to particle size and shape, which determine how the free electrons are polarized and distributed on the surface. As a consequence, control of the size and shape of plasmonic nanoparticles represents the most powerful means to tailor and finely tune their optical properties. In this chapter, a few among the most important techniques enabling size/shape-controlled growth of metal nanoparticles will be reviewed. Some examples of postsynthesis nanoparticle purification and surface modification toward plasmonic applications will also be provided.

Nanomaterials offer unique properties that bridge classic to quantum behavior of matter. Gold nanoparticles (GNPs) are a relevant class of nanomaterials that has gained considerable attention for potential applications in medicine due to their size-dependent electronic, optical, and chemical properties. Gold nanorods (GNRs) are intriguing anisotropic-shaped type of GNPs with unique optical and photo-thermal properties used in many research fields such as optics, photonics, and nanomedicine. Particularly, under a suitable optical radiation, the GNRs feature enhanced light absorption, turning it into an ideal nano-source of heat, remotely controllable by exploiting light. In this framework, we have achieved a breakthrough in monitoring photo-induced nanoscale temperature variation by combining GNRs and thermotropic cholesteric liquid crystals. Investigation of morphological and optical properties of the obtained material reveals an original and efficient tool to detect temperature variationsat the nanoscale.

Nanomaterials represent a class of materials based on nanoscale structures. Nanomaterials are currently used in a wide variety of applications, including, optoelectronics, energy conversion, biology health care and medicine. Among different types of nanomaterials, gold nanoparticles have received considerable attention in disease diagnosis and therapy due to their optical and chemical properties (Liz-Marzan in Mater Today 7:26–31, 2004). This paper reports the main optical and photo-thermal properties of gold nanoparticles. Particularly, we show that gold nanorods embedded in cholesteric liquid crystals demonstrate to control the “selective reflection” of a light beam. Investigation of the optical properties of the obtained material reveals an original and efficient tool to detect temperature variations at the nanoscale useful for photo-thermal based therapies applications. Finally, the concept of ‘nanoparticle-protein corona interaction can be exploited for application ranging from regenerative medicine to theranostics.

A liquid crystalline, negatively charged, whole-genome DNA is exploited to organize positively charged gold nanorods (GNRs) by means of electrostatic interaction. A mesoscopic alignment of the composite system along a preferred direction is obtained by casting a droplet of the DNA-nanorods solution onto an untreated glass substrate. Gel electrophoresis analysis enables evaluating the effective electric charge of the system, thus minimizing the DNA fragmentation. Polarized optical microscopy, combined with transmission and scanning electron microscopy, shows that, up to 20% in weight of GNR solution, the system exhibits both a long range order, induced by the liquid crystalline phase of the DNA, and a nanoscale organization, due to the DNA self-assembly. These evidences are confirmed by a polarized spectral analysis, which also points out that the optical properties of GNRs strongly depend on the polarization of the impinging probe light. The capability to organize plasmonic nanoparticles by means of DNA material represents a significant advance towards the realization of life science inspired optical materials.

Controlling light interactions with matter on the nanometer scale provides for compelling opportunities for modern technology and stretches our understanding and exploitation of applied physics, electronics, and fabrication science. The smallest size to which light can be confined using standard optical elements such as lenses and mirrors is limited by diffraction. Plasmonic nanostructures have the extraordinary capability to control light beyond the diffraction limit through an unique phenomenon called the localized plasmon resonance. This remarkable capability enables unique prospects for the design, fabrication and characterization of highly integrated photonic signal-processing systems, nanoresolution optical imaging techniques and nanoscale electronic circuits. This paper summarizes the basic principles and the main achievements in the practical utilization of plasmonic effects in nanoparticles. Specifically, the paper aims at highlighting the major contributions of nanoparticles to nanoscale temperature monitoring, modern “drug free” medicine and the application of nanomaterials to a new generation of opto-electronics integrated circuits.

Nanostructured films based on Au nanorods (NRs) have been obtained by layer-by-layer (LbL) assembly driven by electrostatic interaction between metal nanoparticles and polyelectrolytes. Multilayer films have been fabricated by using LbL assembly of poly(sodium styrenesulfonate) (PSS) and positively charged Au NRs on a polyelectrolyte-modified substrate. The effect of fabrication parameters, including the nature of the substrate, the polyelectrolyte initial anchoring layer, and the number of layers has been investigated by means of UV-vis absorbance spectroscopy and atomic force microscopy (AFM). The results demonstrated the dependence of morphology and plasmonic features in the multilayered nanostructured architectures from the nature of the anchoring polyelectrolyte on the substrate, the number of layers, and the kind of NR mutual assembly. In addition, a study of the electrochemical activity at the solid/liquid interface has been carried out in order to assess charge transport through the NR multilayer by using two molecular probes in solution, namely, potassium ferricyanide, a common and well-established redox mediator with reversible behavior, and cytochrome C, a robust model redox protein. The presented systematic study of the immobilization of Au NRs opens the venue to several application areas, such as (bio)chemical sensing.

The amplification of Raman signals of the heteroaromatic cation 1-(N-methylpyrid-4-yl)-2-(N-methylpyrrol-2-yl)ethylene (PEP+)) bound to Au nanorods (NRs) was investigated at different excitation wavelengths to study the effect of the laser resonance with the absorption band of the PEP+ moiety and with the two plasmon oscillation modes of the NR. Two different PEP+ derivatives, differing in the length of the alkyl chain bearing the anchoring group, were used as target molecules. Raman spectra obtained exciting at 514 or at 785 nm (i.e., exciting the transverse or the longitudinal plasmon band) present a higher intensity than that at 488 nm suggesting a higher Raman amplification when the laser excitation wavelength is resonant with one of the two plasmon modes. Moreover, considering results of Discrete Dipole Approximation (DDA) calculations of the local field generated at the NR surface when either the transverse or the longitudinal plasmon modes are excited, we deduced that the resonance condition of the 514-nm laser excitation with the absorption band of the dye strongly contributes to the amplification of the Raman signal. © 2014 The Author(s).

Photosystem II (PSII) proteins from spinach leaves were immobilized onto quartz substrates according to the Layer-by-Layer (LbL) procedure, alternating protein to polyethylenimine (PEI) layers by exploiting electrostatic interactions. The effects of several factors, such as storage conditions, ageing of the PSII-modified substrates, as well as PSII concentration in buffer, on the quality of the prepared multilayers, were investigated by UV-vis Absorption Spectroscopy and Atomic Force Microscopy (AFM). A number of 13 layers was found to be optimal to guarantee intense PSII optical signals with homogeneous morphological distributions of proteins. The multilayers resulted stable if stored in contact with air at 4 degrees C, as observed by UV-vis Absorption spectra recorded after 48 h. The best results in terms of AFM images and electron transfer efficiency (measured by Hill Reaction assays) were gained by using 5.6 x 10(-7) M chlorophyll concentration, obtaining multilayers with the most ordered protein distributions and the highest electron transfer efficiency, i.e. 85 % of an iso-absorbing PSII suspension. The results highlight the possibility to successfully immobilize PSII proteins, without considerable loss of bioactivity, thanks to the mild nature of the electrostatic LbL technique, opening up possibilities of applications in the bioelectrochemical energy conversion and biosensoristic fields.

A simple and low cost strategy for heavy metal sensing based on an easy and reliable colorimetric detection was investigated by using water soluble gold nanorods (Au NRs), functionalized with L-cysteine. Detection tests have been performed on several heavy metal ions, namely Zn2+, Cd2+, Hg2+, Cu2+, Pb2+ and As3+ ions and monitored by UV-Vis absorption spectroscopy and transmission electron microscopy (TEM). The system has demonstrated a remarkable sensitivity for Hg2+ with limit of detection (LOD) at ppt level. A red-shift in the maximum of the typical longitudinal plasmon band of Au NRs has been observed and recognized related to aggregation phenomena occurring among Au NRs only in presence of Hg2+ ions. Interestingly, a significantly different response is recorded for the other tested heavy metal ions. The results highlight that the functionalization of Au NRs with L-cysteine is an excellent route to implement a reliable colorimetric sensing device, able to push further down the detection limit recorded for similar strategies based on spherical Au NPs.

Strong enhancements in the spontaneous emission intensity of dye chromophores-loaded in a printable polymer have been achieved by coupling the dye emission to surface plasmons of metallic thin films and metallic nanoparticles. The nanocomposite materials embossed by nanoimprint lithography process show good imprint properties.

Water-soluble gold nanorods (Au NRs) were synthesized using a silver-ion mediated photochemical route under UV irradiation. Extended X-ray Absorption Fine Structure (EXAFS) measurements on the Ag K-edge were performed on samples obtained at different Ag/Au ratios and at increasing irradiation times in order to investigate the fate of silver ions during the growth of Au NRs. EXAFS measurements allowed to probe the chemical state and the local environment of silver in the final product. Experimental data suggest that Ag atoms are placed on top of the Au particles as metallic Ag(0), while no significant contribution to the EXAFS spectra comes from AgBr or other Ag(+) based species. The reported results strongly support the deposition of Ag(0) islands on the (110) surfaces of the Au particles, thus driving the anisotropic growth via the (111) surfaces.

The role of Ag+ ions in the ultraviolet-driven photochemical synthesis of Au nanorods (NRs) in aqueous surfactant mixtures has been investigated in order to elucidate the mechanism that drives anisotropic nanoparticle growth. The samples, grown in the presence of varying amounts of Ag+ ions for scheduled irradiation times, have been characterized by ultraviolet−visible−near infrared (UV−vis−NIR) absorption spectroscopy, analytical transmission electron microscopy (ATEM), inductively coupled plasma atomic emission spectroscopy (ICP-AES), and extended X-ray absorption fine structure (EXAFS) measurements. Moreover, the time evolution of size and shape distribution has been investigated by statistical analysis of the relevant TEM data. EXAFS measurements at the Ag K-edge have unambiguously disclosed the presence of Ag species in the final product, identifying their chemical state as well as the most probable lattice environment around them with a reasonably high level of confidence. The extensive sample knowledge gained by the combination of spectroscopic, structural, and morphological measurements has provided reliable information regarding the most relevant processes underlying the Ag+-assisted formation of Au NRs by the photochemical route. An induction period prior to occurrence of fast nanoparticle nucleation has been identified, which has been correlated to the slow accumulation of a critical concentration of Au(I)−surfactant species from reduction of their Au(III) parent precursors. The role played by Ag in directing Au growth toward the formation of NRs has been clarified through demonstration of preferential adsorption of zerovalent Ag species on {110} facets of the growing Au nanoparticles, which can be therefore responsible for restricting crystal development along the relevant crystallographic directions.

A 1.7-fold enhancement in the spontaneous emission intensity of dye chromophore loaded in a printable polymer is achieved by coupling the dye emission to surface plasmons of metallic nanoparticles. The nanocomposite material, embossed into arrays of wires by nanoimprint lithography process, shows good imprint properties. The results prove the potential of the prepared luminescent functional materials for micro- and nanofabrication and suggest the use of nanocomposite materials in prospective nanoplasmonic applications.