Structural and optical properties of novel surfactant-coated Yb@TiO<Subscript>2</Subscript> nanoparticles

In this paper a novel hybrid approach to synthesise composite nanoparticles is presented. It is based on the laser ablation of a bulk target (Yb) immersed in a reversed micellar solution which contains nanoparticles of a different host material (TiO₂ nanoparticles) previously synthesised by chemical method. This approach thus exploits the advantages of the chemical synthesis through reversed micellar solution (size control, nanoparticle stabilisation), and of the laser ablation (“clean” synthesis, no side reactions). Central role is played by the microscopic processes controlling the deposition of the ablated Yb atoms onto the surface of TiO₂ nanoparticles which actually behave as nucleation seeds. The structural features of the resulting Yb@TiO₂ composite nanoparticles have been studied by Transmission Electron Microscopy, whereas their peculiar optical properties have been explored by UV–Vis spectroscopy and steady-state fluorescence. Results consistently show the formation of Yb and TiO₂ glued nanodomains to form nearly spherical and non-interacting nanoparticles with enhanced photophysical properties.     

Quantitative polymerase chain reaction and microchip electrophoresis to detect major rearrangements of the low-density lipoprotein receptor gene causing familial hypercholesterolemia

A variety of rearrangements in the low-density lipoprotein receptor (LDLR) gene cause severe forms of familial hypercholesterolemia (FH). However, current methods for searching these abnormalities in FH samples, e.g., Southern and Northern Blot, are labor-intensive and not routinely used by diagnostic laboratories. We developed a simpler approach based on the quantitative polymerase chain reaction (PCR) amplification of part or all gene's coding sequences by a series of multiplex amplifications comprising three nonadjacent gene sections plus a fourth section used as an internal reference. Thereafter, the analysis of these PCR products by microchip electrophoresis revealed either deletions or duplications in the investigated gene sections through the simple comparison of electropherograms obtained from mutant and control samples. This required primers leading to well-resolved peaks with minimal size differences among coamplified products and PCR conditions allowing a linear quantitative response to template amount variations as those caused by duplication or deletion of specific gene sections. Also, the inclusion of exon 17 amplification product as an internal reference in each multiplex PCR allowed the normalization of quantitative results by dividing the area of each amplified section by the area of exon 17. The comparison of these ratios calculated from 10 carriers of 6 LDLR known rearrangements with those obtained from 14 control samples showed that gross deletions roughly halved and duplications doubled the ratio values of exons involved in the mutation. This allowed to distinguish gross mutations from sample-to-sample differences that reached at maximum 8% variation over mean values.     

The electrochemistry of gold in acetonitrile solutions containing thiocyanate ions

Gold dissolves anodically in acetonitrile solutions containing dissolved NaSCN, at 25°C. The reaction yields Au(I) and Au(III) complex ion species which can be cathodically electroplated. The voltammetric experiments indicate that the anodic dissolution is preceded by a partial surface saturation with the intermediate initially discharged, followed by a diffusion controlled process which depends on the SCN^? ion concentration. The electrochemical behaviour of the anodic and cathodic processes is comparable to that of gold in aqueous solutions containing Au-complex ions.     

Optically Transparent Gold Nanoparticles for DSSC Counter-Electrode: An Electrochemical Characterization

A gold nanoparticles transparent electrode was realized by chemical reduction. This work aims to compare the transparent gold nanoparticles electrode with a more commonly utilized gold-film-coated electrode in order to investigate its potential use as counter-electrode (CE) in dye-sensitized solar cells (DSSCs). A series of DSSC devices, utilizing I⁻/I³⁻ and Co(III)/(II) polypyridine redox mediators [Co(dtb)3]³⁺/²⁺; dtb = 4,4′ditert-butyl-2,2′-bipyridine)], were evaluated. The investigation focused firstly on the structural characterization of the deposited gold layers and then on the electrochemical study. The novelty of the work is the realization of a gold nanoparticles CE that reached 80% of average visible transmittance. We finally examined the performance of the transparent gold nanoparticles CE in DSSC devices. A maximum power conversion efficiency (PCE) of 4.56% was obtained with a commercial I⁻/I³⁻-based electrolyte, while a maximum 3.1% of PCE was obtained with the homemade Co-based electrolyte.     

Micro‐Raman innovative methodology to identify Ag–Cu mixed sulphides as tarnishing corrosion products

Mixed Cu–Ag alloys with different compositions have been produced and subjected to an accelerated sulphidation process which causes the development of a mixed sulphide‐rich corroded film on their surface. It was called tarnishing, that is, the formation of a blue‐brownish patina when Cu–Ag alloys are exposed in a sulfur‐containing atmosphere. The structures of the pristine alloys have been determined by the combined analytical techniques as scanning electron microscopy energy dispersive X‐ray microanalysis and X‐ray diffraction. The experimental conclusions confirmed the occurrence of micro phase separation with the formation of different dendritic domains of about 10 µm in width. The sulphidized samples were firstly investigated by optical microscopy and X‐ray diffraction in order to verify the homogeneity of the patina and to identify the different AgCuS phases appearing on the alloy surfaces. It was observed that, despite the inherent micro‐heterogeneity of the alloys, the sulphide layer was throughout uniform in composition at the micro‐scale. The complex scenario of the relative stability of all the various mixed sulphides involved was then explored by micro‐Raman spectroscopy (μ‐RS), pointing out that the Cu‐for‐Ag substitution in the crystal lattice of the mixed Ag–Cu sulphides caused a monotonous blue shift of the vibrational wavenumbers in Raman spectra. This study has unveiled microscopic details of the tarnishing process, furnishing an innovative, cheap and non‐destructive methodology based on μ‐Raman spectroscopy for the evaluation of the silver‐copper artefacts via the compositions of their corroded products. Copyright © 2016 John Wiley & Sons, Ltd.     

Structural and Optical Properties of Novel Surfactant Coated TiO<Subscript>2</Subscript>–Ag Based Nanoparticles

Stable dispersions of surfactant-coated TiO₂–Ag based nanoparticles in apolar medium have been prepared by performing sequentially the hydrolysis of titanium(IV) isopropoxide and the reduction of Ag⁺ in the confined space of sodium bis(2-ethylhexyl)sulfosuccinate (NaAOT) reverse micelles. Depending on the sequence length, this novel procedure allowed the synthesis of semiconductor–metal nanoparticles, nominally indicated as TiO₂/Ag, TiO₂/Ag/TiO₂, and TiO₂/Ag/TiO₂/Ag, stabilized by a monolayer of oriented surfactant molecules. The structural characterization of these nanoparticles has been performed by High Resolution Transmission Electron Microscopy (HR-TEM), while optical properties were investigated by UV–Vis absorption and fluorescence spectroscopies. TEM investigation showed the presence of globular nanoparticles with an average diameter of about 10 nm composed by distinct amorphous TiO₂ and crystalline Ag glued domains whose structure depends on the sequence length. UV–Vis absorption measurements highlighted the mutual metal–semiconductor influence on the TiO₂ energy band gap and on the Ag plasmon resonance. Steady-state fluorescence spectra analysis allowed to reveal the strong inhibition of the electron–hole radiative recombination in the TiO₂ domains due to the Ag and the appearance of a new emission band centred in the 484–545 nm range. Possible attributions of the involved electronic transition of this last emission are discussed.