Raman and DFT study of methimazole chemisorbed on gold colloidal nanoparticles

The adsorption of methimazole on gold colloidal nanoparticles was investigated using a combination of surface-enhanced Raman scattering and density functional theory calculations, which allowed identifying the thiolate anion as the molecular species chemically interacting with the active sites of the gold surface, modeled as zero-charge metal adatoms, only through the sulfur atom. This result can be important for the use of these ligand/metal nanohybrids in the process of drug delivery. Moreover, functionalized gold nanoparticles are able to promote the Raman enhancement in the red-light region as well as in the near-infrared, where generally no fluorescence emission occurs. This paves the way for the use of these nanosystems in a biological environment, even in vivo experiments

Spectroscopic and microscopic analyses of Fe3O4/au nanoparticles obtained by laser ablation in water

Magneto-plasmonic nanoparticles constituted of gold and iron oxide were obtained in an aqueous environment by laser ablation of iron and gold targets in two successive steps. Gold nanoparticles are embedded in a mucilaginous matrix of iron oxide, which was identified as magnetite by both microscopic and spectroscopic analyses. The plasmonic properties of the obtained colloids, as well as their adsorption capability, were tested by surface-enhanced Raman scattering (SERS) spectroscopy using 2,2′-bipyridine as a probe molecule. DFT calculations allowed for obtaining information on the adsorption of the ligand molecules that strongly interact with positively charged surface active sites of the gold nanoparticles, thus providing efficient SERS enhancement. The presence of iron oxide gives the bimetallic colloid new possibilities of adsorption in addition to those inherent to gold nanoparticles, especially regarding organic pollutants and heavy metals, allowing to remove them from the aqueous environment by applying a magnetic field. Moreover, these nanoparticles, thanks to their low toxicity, are potentially useful not only in the field of sensors, but also for biomedical applications

Palladium oxide nanoparticles: Preparation, characterization and catalytic activity evaluation

Stable palladium oxide nanoparticles were prepared in aqueous suspension with a very simple procedure, by dissolving palladium nitrate in water at a concentration around 10-4 M. UV-visible absorption spectroscopy was adopted to follow the formation of these nanoparticles, which were characterized by TEM microscopy, along with XRD, XPS and Raman measurements. DFT calculations allowed to interpret the Raman data and to clarify the species present at the surface of the nanoparticles. The catalytic activity of the latter was evaluated by monitoring the reduction of p-nitrophenol to p-aminophenol. This investigation paves the way to the use of these colloidal nanoparticles in processes of heterogeneous catalysis, in particular those concerning the catalytic degradation of aromatic derivatives that represent a serious danger for the environment as pollutants, as in the case of p-nitrophenol

SERS, XPS and DFT study of xanthine adsorbed on citrate-stabilized gold nanoparticles

We have studied the adsorption of xanthine, a nucleobase present in human tissue and fluids that is involved in important metabolic processes, on citrate-reduced gold colloidal nanoparticles by means of surface-enhanced Raman scattering (SERS), absorption, and X-ray photoelectron spectroscopy (XPS) measurements, along with density functional theory (DFT) calculations. The citrate anions stabilize the colloidal suspensions by strongly binding the gold nanoparticles. However, these anions do not impair the adsorption of xanthine on positively-charged active sites present on the metal surface. We have obtained the Fourier transform (FT)-SERS spectra of adsorbed xanthine by laser excitation in the near infrared spectral region, where interference due to fluorescence emission does not usually occur. In fact, the addition of chloride ions to the Au/xanthine colloid induces the aggregation of the gold nanoparticles, whose plasmonic band is shifted to the near infrared region where there is the exciting laser line of the FT\u2013Raman instrument. Hence, this analytical approach is potentially suitable for spectroscopic determination of xanthine directly in body fluids, avoiding fluorescence phenomena induced by visible laser irradiation

Computational Approaches to the Electronic Properties of Noble Metal Nanoclusters Protected by Organic Ligands

Organometallic nanoparticles composed by metal cores with sizes under two nanometers covered with organic capping ligands exhibit intermediate properties between those of atoms and molecules on one side, and those of larger metal nanoparticles on the other. In fact, these particles do not show a peculiar metallic behavior, characterized by plasmon resonances, but instead they have nonvanishing band-gaps, more along molecular optical properties. As a consequence, they are suitable to be described and investigated by computational approaches such as those used in quantum chemistry, for instance those based on the time-dependent density functional theory (TD-DFT). Here, I present a short review of the research performed from 2014 onward at the University of Modena and Reggio Emilia (Italy) on the TD-DFT interpretation of the electronic spectra of different organic-protected gold and/or silver nanoclusters

Modelling of spectroscopic and structural properties using molecular dynamics

The work described here was carried out at the European Lab. for Non-Linear Spectroscopy (LENS) to achieve a better understanding of molecular vibrations employing computer simulations. H-bonds are the main intermolecular interactions affecting vibrational spectra and here it’s shown how they usually induce a (red or blue) shift on the vibrational frequencies of the groups engaged in them, and how this shift nicely correlates with structural properties. H-bonds can be present also in a bifurcated arrangement. In systems such as confined water, this bifurcated configuration has long lifetimes, allowing it to be studied by both spectroscopic and computational means. The computational protocols implemented and adopted here allow for a direct comparison between structural features and vibrational spectra

Can DFT Calculations Provide Useful Information for SERS Applications?

: Density functional theory (DFT) calculations allow us to reproduce the SERS (surface-enhanced Raman scattering) spectra of molecules adsorbed on nanostructured metal surfaces and extract the most information this spectroscopy is potentially able to provide. The latter point mainly concerns the anchoring mechanism and the bond strength between molecule and metal as well as the structural and electronic modifications of the adsorbed molecule. These findings are of fundamental importance for the application of this spectroscopic technique. This review presents and discusses some SERS-DFT studies carried out in Italy as a collaboration between the universities of Modena and Reggio-Emilia and of Florence, giving an overview of the information that we can extract with a combination of experimental SERS spectra and DFT modeling. In addition, a selection of the most recent studies and advancements on the DFT approach to SERS spectroscopy is reported with commentary

DFT and TD-DFT Study of the Chemical Effect in the SERS Spectra of Piperidine Adsorbed on Silver Colloidal Nanoparticles

The surface-enhanced Raman scattering (SERS) spectra of piperidine adsorbed on silver/chloride colloids were studied by a combined density functional theory (DFT)/time dependent DFT (TD-DFT) approach. The mechanism of chemical enhancement on the Raman signals is due to at least two contributions: the first comes from the changes in the molecular force constants and the dynamic polarizabilities of the normal modes, when the molecule is chemisorbed. DFT calculations satisfactorily reproduce the SERS spectra of piperidine adsorbed on silver, showing that the species formed on the silver particle is a complex formed by a deprotonated piperidine linked to a silver cation. A second contribution to the SERS chemical enhancement is due to a resonance Raman effect occurring when the wavelength of the Raman excitation falls within the electronic excitation band of the molecule/metal complex. Actually, the SERS spectra of piperidine show a significant dependence on the wavelength of the laser excitation, with a marked enhancement in the green-light region. TD-DFT calculations on the most-probable complex explain this behavior, because a strong excitation band of the complex is calculated in the green spectral region. This pinpoints that a resonance between the exciting radiation and the absorption band of this complex is responsible for this enhancement effect

Integrated Water Resources Management in Federations: The Examples of Brazil and Switzerland

International water institutions worldwide consider integrated water resources management (IWRM) to be the most sustainable way to manage water. Governments have modified their legal and institutional framework in order to apply integrated water management tools in the river basin. Institutional challenges are common in federations due to complex power sharing at national and subnational levels. This article discusses the implementation of the hegemonic model of IWRM in federations, based on a review of the literature for two different federal countries: Brazil and Switzerland. Due to the centralized character of Brazilian federalism, adjustments made in recent decades aimed to adapt the water management model through a hegemonic approach of participation and decentralization, shaped by international experiences and institutions. Some challenges concern vertical interplay, concerning coordination between levels and effective implementation of decentralization and participation. In contrast, Switzerland has a non-hegemonic model of water management, which is varied and fragmented throughout the country. As management is decided and applied locally, the main challenge concerns horizontal interplay, with regionalization and coordination of water uses

A DFT approach to the surface-enhanced raman scattering of 4-cyanopyridine adsorbed on silver nanoparticles

A Surface-Enhanced Raman Scattering (SERS) spectrum of 4-cyanopyridine (4CNPy) was recorded on silver plasmonic nanoparticles and analyzed by using Density Functional Theory (DFT) calculations. Two simple molecular models of the metal\u20134CNPy surface complex with a single silver cation or with a neutral dimer (Ag+ \u20134CNPy, Ag2 \u20134CNPy), linked through the two possible interacting sites of 4CNPy (aromatic nitrogen, N, and nitrile group, CN), were considered. The calculated vibrational wavenumbers and intensities of the adsorbate and the isolated species are compared with the experimental Raman and SERS results. The analysis of the DFT predictions and the experimental data indicates that 4CNPy adsorbs preferentially on neutral/charged active sites of the silver nanoparticles through the nitrogen atom of the aromatic ring with a perpendicular orientation