Advanced Synchrotron Radiation Techniques for Nanostructured Materials

Nanostructured materials exploit physical phenomena and mechanisms that cannot be derived by simply scaling down the associated bulk structures and phenomena; furthermore, new quantum effects come into play in nanosystems. The exploitation of these emerging nanoscale interactions prompts the innovative design of nanomaterials. Understanding the behavior of materials on all length scales—from the nanostructure up to the macroscopic response—is a critical challenge for materials science. Modern analytical technologies based on synchrotron radiation (SR) allow for the non-destructive investigation of the chemical, electronic, and magnetic structure of materials in any environment. SR facilities have developed revolutionary new ideas and experimental setups for characterizing nanomaterials, involving spectroscopy, diffraction, scatterings, microscopy, tomography, and all kinds of highly sophisticated combinations of such investigation techniques. This book is a collection of contributions addressing several aspects of synchrotron radiation as applied to the investigation of chemical, electronic, and magnetic structure of nanostructured materials. The results reported here provide not only an interesting and multidisciplinary overview of the chemicophysical investigations of nanostructured materials carried out by state-of-the-art SR-induced techniques, but also an exciting glance into the future perspectives of nanomaterial characterization methods

Sensitivity of Hydra vulgaris to Nanosilver for Environmental Applications

Nanosilver applications, including sensing and water treatment, have significantly increased in recent years, although safety for humans and the environment is still under debate. Here, we tested the environmental safety of a novel formulation of silver nanoparticles functionalized with citrate and L-cysteine (AgNPcitLcys) on freshwater cnidarian Hydra vulgaris as an emerging ecotoxicological model for the safety of engineered nanomaterials. AgNPcitLcys behavior was characterized by dynamic light scattering (DLS), while Ag release was measured by inductively coupled plasma mass spectrometry (ICP-MS). H. vulgaris (n = 12) subjects were evaluated for morphological aberration after 96 h of exposure and regeneration ability after 96 h and 7 days of exposure, after which the predatory ability was also assessed. The results show a low dissolution of AgNPcitLcys in Hydra medium (max 0.146% of nominal AgNPcitLcys concentration) and highlight a lack of ecotoxicological effects, both on morphology and regeneration, confirming the protective role of the double coating against AgNP biological effects. Predatory ability evaluation suggests a mild impairment of the entangling capacity or of the functionality of the tentacles, as the number of preys killed but not ingested was higher than the controls in all exposed animals. While their long-term sub-lethal effects still need to be further evaluated on H. vulgaris, AgNPcitLcys appears to be a promising tool for environmental applications, for instance, for water treatment and sensing

Observing thermal lensing with quantum light

The introduction of quantum methods in spectroscopy can provide enhanced performance and technical advantages in the management of noise. We investigate the application of quantum illumination in a pump and probe experiment. Thermal lensing in a suspension of gold nanorods is explored using a classical beam as the pump and the emission from parametric downconversion as the probe. We obtain an insightful description of the behaviour of the suspension under pumping with a method known to provide good noise rejection. Our findings are a further step towards investigating effects of quantum light in complex plasmonic media

Core shell hybrids based on noble metal nanoparticles and conjugated polymers: synthesis and characterization

Noble metal nanoparticles of different sizes and shapes combined with conjugated functional polymers give rise to advanced core shell hybrids with interesting physical characteristics and potential applications in sensors or cancer therapy. In this paper, a versatile and facile synthesis of core shell systems based on noble metal nanoparticles (AuNPs, AgNPs, PtNPs), coated by copolymers belonging to the class of substituted polyacetylenes has been developed. The polymeric shells containing functionalities such as phenyl, ammonium, or thiol pending groups have been chosen in order to tune hydrophilic and hydrophobic properties and solubility of the target core shell hybrids. The Au, Ag, or Pt nanoparticles coated by poly(dimethylpropargylamonium chloride), or poly(phenylacetylene-co-allylmercaptan). The chemical structure of polymeric shell, size and size distribution and optical properties of hybrids have been assessed. The mean diameter of the metal core has been measured (about 10-30 nm) with polymeric shell of about 2 nm

Oxidized Palladium Supported on Ceria Nanorods for Catalytic Aerobic Oxidation of Benzyl Alcohol to Benzaldehyde in Protic Solvents

In the present study, the catalytic activity of palladium oxide (PdOx) supported on ceria nanorods (CeO2-NR) for aerobic selective oxidation of benzyl alcohol (BnOH) to benzaldehyde (PhCHO) was evaluated. The CeO2-NR was synthesized hydrothermally and the Pd(NO3)2 was deposited by a wet impregnation method, followed by calcination to acquire PdOx/CeO2-NR. The catalysts were characterized by X-ray diffraction (XRD), temperature programmed reduction (TPR), transmission electron microscopy (TEM), Brunauer–Emmet–Teller (BET) surface area analysis, and X-ray photoelectron spectroscopy (XPS). In addition, the TPR-reduced PdOx/CeO2-NR (PdOx/CeO2-NR-Red) was studied by XRD, BET, and XPS. Characterizations showed the formation of CeO2-NR with (111) exposed plane and relatively high BET surface area. PdOx (x > 1) was detected to be the major oxide species on the PdOx/CeO2-NR. The activities of the catalysts in BnOH oxidation were evaluated using air, as an environmentally friendly oxidant, and various solvents. Effects of temperature and palladium oxidation state were investigated. The PdOx/CeO2-NR showed remarkable activity when protic solvents were utilized. The best result was achieved using PdOx/CeO2-NR and boiling ethanol as solvent, leading to 93% BnOH conversion and 96% selectivity toward PhCHO. A mechanistic hypothesis for BnOH oxidation with PdOx/CeO2-NR in ethanol is presente

Fast remote spectral discrimination through ghost spectrometry

Assessing the presence of chemical, biological, radiological and nuclear threats is a crucial task which is usually dealt with by analyzing the presence of spectral features in a measured absorption profile. The use of quantum light allows to perform these measurements remotely without compromising the measurement accuracy through ghost spectrometry. However, in order to have sufficient signal-to-noise ratio, it is typically required to wait long acquisition times, hence subtracting to the benefits provided by remote sensing. In many instances, though, reconstructing the full spectral lineshape of an object is not needed and the interest lies in discriminating whether a spectrally absorbing object may be present or not. Here we show that this task can be performed fast and accurately through ghost spectrometry by comparing the low resources measurement with a reference. We discuss the experimental results obtained with different samples and complement them with simulations to explore the most common scenarios

Dye-Doped Polymeric Microplastics: Light Tools for Bioimaging in Test Organisms

Ecosystems around the world are experiencing a major environmental impact from microplastic particles (MPs 0.1 & mu;m-1 mm). Water, sediments, and aquatic biota show the widespread presence of this pollutant. However, MPs are rarely used in laboratory studies as they are scarcely available for purchase or expensive, especially if one wishes to trace the particle with a dye or fluorescent. Furthermore, existing preparation techniques have limited application in biological studies. In this work, we propose a new, easy, and cheap way to prepare fluorescent MPs. The protocol is based on the osmosis method in order to obtain spherical polymeric particles of P(S-co-MMA), with 0.7-9 micron diameter, made fluorescent because dye-doped with rhodamine B isothiocyanate (RITC) or fluorescein isothiocyanate (FITC). The dye loading was studied and optimized, and the MPs-dye conjugates were characterized by UV-vis FTIR and XPS spectrometry and scanning electron microscopy (SEM). Furthermore, preliminary tests on aquatic organisms demonstrated the possible use of these fluorescent MPs in bioimaging studies, showing their absorption/adsorption by duckweeds (Lemna minuta) and insect larvae (Cataclysta lemnata)

Synthesis and Microstructural Investigations of Organometallic Pd(II) Thiol-Gold Nanoparticles Hybrids

In this work the synthesis and characterization of gold nanoparticles functionalized by a novel thiol-organometallic complex containing Pd(II) centers is presented. Pd(II) thiol,trans, trans-[dithiolate-dibis(tributylphosphine)dipalladium(II)-4,4′-diethynylbiphenyl] was synthesized and linked to Au nanoparticles by the chemical reduction of a metal salt precursor. The new hybrid made of organometallic Pd(II) thiol-gold nanoparticles, shows through a single S bridge a direct link between Pd(II) and Au nanoparticles. The size-control of the Au nanoparticles (diameter range 2–10 nm) was achieved by choosing the suitable AuCl4−/thiol molar ratio. The size, strain, shape, and crystalline structure of these functionalized nanoparticles were determined by a full-pattern X-ray powder diffraction analysis, high-resolution TEM, and X-ray photoelectron spectroscopy. Photoluminescence spectroscopy measurements of the hybrid system show emission peaks at 418 and 440 nm. The hybrid was exposed to gaseous NOxwith the aim to evaluate the suitability for applications in sensor devices; XPS measurements permitted to ascertain and investigate the hybrid –gas interaction