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

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

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

Water Supply Basins of São Paulo Metropolitan Region: Hydro-Climatic Characteristics of the 2013–2015 Water Crisis

São Paulo metropolitan region experienced an acute water crisis between 2013 and 2015. According to the Brazilian and international press, it was due to climatic, anthropogenic, and water management factors. This paper assesses the hydro-climatic characteristics of the crisis by focusing on the Alto-Tietê basin and the headwater of the Piracicaba-Capivari-Jundiaí (PCJ) basin that supply 70% of the water consumed in the metropolis. Based on 16 rain-gauge stations, 5 runoff-gauge stations, and several statistical analyses carried over the 1951–2015 period, this assessment shows that the 2013–2015 hydro-climatic crisis resulted from a large number of days without rain in the north of the Alto-Tietê basin and to less intense precipitation events in the headwaters of the PCJ basin during the austral spring 2013 and the year 2014. It also defines a return period of 98 years for observed river flows in 2014. Despite the rare nature of this hydrological drought, the need for efficient water saving policies is brought forward

Tandem chemiluminescence-flow injection analysis for dimethoate determination

This work was supported by the Ministry of Education and Science of Spain (Project CTM2006-11991) and FEDER funds.Catalá Icardo, M.; López Paz, JL.; Choves Barón, C. (2010). Tandem chemiluminescence-flow injection analysis for dimethoate determination. Luminescence. 25:235-236. https://doi.org/10.1002/bio.1217S2352362

Capture Velocity for a Magneto-Optical Trap in a Broad Range of Light Intensity

In a recent paper, we have used the dark-spot Zeeman tuned slowing technique [Phys. Rev. A 62, 013404-1, (2000)] to measure the capture velocity as a function of laser intensity for a sodium magneto optical trap. Due to technical limitation we explored only the low light intensity regime, from 0 to 27 mW/cm^2. Now we complement that work measuring the capture velocity in a broader range of light intensities (from 0 to 400 mW/cm^2). New features, observed in this range, are important to understant the escape velocity behavior, which has been intensively used in the interpretation of cold collisions. In particular, we show in this brief report that the capture velocity has a maximum as function of the trap laser intensity, which would imply a minimum in the trap loss rates.Comment: 2 pages, 2 figure

Raman and Computational Study on the Adsorption of Xanthine on Silver Nanocolloids

Xanthine is a nucleobase, deriving from adenine and guanine by deamination and oxidation processes, which may deposit in the human body causing diseases, similar to uric acid. Here, we have investigated the adsorption of xanthine on silver colloidal nanoparticles by means of surface-enhanced Raman scattering (SERS) with an exciting radiation in the near-infrared spectral region, where interference due to fluorescence does not occur, along with density functional theory calculations of molecule/metal model systems. By adopting a combined experimental and computational approach, we have identified the "marker" SERS bands of xanthine and the tautomer that preferentially binds the silver particles, as well as the molecular group involved in the interaction with metal. This investigation allows using the FT-SERS spectroscopy for biosensory and diagnostic purposes in body fluids, detecting abnormal levels of xanthine, and preventing metabolic diseases

Elucidation of the pre-nucleation phase directing metal-organic framework formation

Metal-organic framework (MOF) crystallization is governed by molecular assembly processes in the pre-nucleation stage. Yet, unravelling these pre-nucleation pathways and rationalizing their impact on crystal formation poses a great challenge since probing molecular-scale assemblies and macroscopic particles simultaneously is very complex. Herein, we present a multimodal, integrated approach to monitor MOF nucleation across multiple length scales by combining in situ optical spectroscopy, mass spectrometry, and molecular simulations. This approach allows tracing initial metal-organic complexes in solution and their assembly into oligomeric nuclei and simultaneously probing particle formation. During Co-ZIF-67 nucleation, a metal-organic pool forms with a variety of complexes caused by ligand exchange and symmetry reduction reactions. We discriminate complexes capable of initiating nucleation from growth species required for oligomerization into frameworks. Co4-nuclei are observed, which grow into particles following autocatalytic kinetics. The geometric and compositional variability of metal-organic pool species clarifies long-debated amorphous zeolitic imidazolate framework (ZIF)-particle nucleation and non-classic pathways of MOF crystallization