Theoretical Design and Experimental Realization of Quasi Single Electron Enhancement in Plasmonic Catalysis

By a combination of theoretical and experimental design, we probed the effect of a quasi‐single electron on the surface plasmon resonance (SPR)‐mediated catalytic activities of Ag nanoparticles. Specifically, we started by theoretically investigating how the E‐field distribution around the surface of a Ag nanosphere was influenced by static electric field induced by one, two, or three extra fixed electrons embedded in graphene oxide (GO) next to the Ag nanosphere. We found that the presence of the extra electron(s) changed the E‐field distributions and led to higher electric field intensities. Then, we experimentally observed that a quasi‐single electron trapped at the interface between GO and Ag NPs in Ag NPs supported on graphene oxide (GO‐Ag NPs) led to higher catalytic activities as compared to Ag and GO‐Ag NPs without electrons trapped at the interface, representing the first observation of catalytic enhancement promoted by a quasi‐single electron.     

A new indirect method based on square-wave voltammetry for ceftiofur determination in bovine milk using an alkaline degradation product

In this paper we present a new electroanalytical method for determination of ceftiofur based on the hydrolysis of this antibiotic in 0.04 mol L⁻¹ Britton–Robinson buffer at pH 10 and 60 °C for 60 min (reduction peak at − 0.70 V). Conditions were optimized for complete hydrolysis and quantitative determination of ceftiofur in milk. The method can be successfully used for determination of the antibiotic directly from samples of fluid milk and powder milk spiked to concentrations of 6.0 × 10⁻⁸, 8.0 × 10⁻⁸, and 10 × 10⁻⁸ mol L⁻¹, respectively. Recovery test ranged from 98.28% to 100.83%. The limits of detection and quantification were 3.73 × 10⁻¹⁰ and 1.24 × 10⁻⁹ mol L⁻¹, respectively. The method has the advantage of eliminating interference from proteins present in the sample, thus obviating the need for exhaustive extraction, which often renders other procedures unfeasible in terms of time and reagent cost. In addition, waste generation was found to be lower than in other methods.     

A Comparative Study of Chemical Routes for Coating Gold Nanoparticles via Controlled RAFT Emulsion Polymerization

The synthesis of core‐shell Au nanoparticles protected by an amphiphilic block copolymer is investigated by distinct reversible addition fragmentation chain transfer (RAFT) emulsion polymerization routes. The controlled polymerization of polymer shells onto Au nanoparticles is attempted by using the macroRAFT (MR) agent based on 2‐(dodecylthiocarbonothioylthio)‐2‐methylpropionic acid synthesized via RAFT polymerization of poly(ethylene glycol) methyl ether acrylate and exploring several approaches, which include (i) post‐modification; (ii) in situ synthesis and (iii) “grafting from” strategies. In the conditions investigated here all these strategies lead to Au polymer nanocomposites but morphological well‐defined core‐shell nanoparticles are only obtained by applying the “grafting from” strategy. In particular, conditions that promote chain extension from the MR agent adsorbed onto the Au nanoparticles are found necessary to obtain nanostructures with such morphological characteristics and that still show the localized surface plasmon resonance typical of colloidal Au nanoparticles.     

Parametric analysis of the growth of colloidal ZnO nanoparticles synthesized in alcoholic medium

The growth kinetics of nanosized ZnO was studied considering the influence of different parameters (mixing degree, temperature, alcohol chain length, reactant concentration and Zn/OH ratios) on the synthesis reaction and modelling the outputs using typical kinetic growth models, which were then evaluated by means of a sensitivity analysis. The Zn/OH ratio, the temperature and the alcohol chain length were found to be essential parameters to control the growth of ZnO nanoparticles, whereas zinc acetate concentration (for Zn/OH = 0.625) and the stirring during the ageing stage were shown to not have significant influence on the particle size growth. This last operational parameter was for the first time investigated for nanoparticles synthesized in 1-pentanol, and it is of outmost importance for the implementation of continuous industrial processes for mass production of nanosized ZnO and energy savings in the process. Concerning the nanoparticle growth modelling, the results show a different pattern from the more commonly accepted diffusion-limited Ostwald ripening process, i.e. the Lifshitz–Slyozov–Wagner (LSW) model. Indeed, this study shows that oriented attachment occurs during the early stages whereas for the later stages the particle growth is well represented by the LSW model. This conclusion contributes to clarify some controversy found in the literature regarding the kinetic model which better represents the ZnO NPs’ growth in alcoholic medium.     

Kinetics of decomposition of alkylammonium salts

The thermogravimetric curves of di-n-propylammonium, di-iso-propylammonium, di-n-butylammonium and di-iso-butylammonium chlorides showed similar profiles, characterized by mass loss in only one stage, corresponding to decomposition of compounds. The following thermal stability order was obtained: [Bu₂ ⁿNH₂]Cl>[Pr₂ ⁿNH₂]Cl>[Pr₂ ⁱNH₂]Cl>[Bu₂ ⁱNH₂]Cl. The values of activation energy for non-isothermal data obtained by Ozawa and Coats-Redfern integral methods were in agreement and stability order obtained by thermogravimetry were reproduced in both methods. The decomposition reactions of [Pr₂ ⁿNH₂]Cl, [Pr₂ ⁱNH₂]Cl and [Bu₂ ⁱNH₂]Cl were better described by A3 model and [Bu₂ ⁿNH₂]Cl by A2 model. This revised version was published online in August 2006 with corrections to the Cover Date.     

Square‐Wave Voltammetry Applied to the Analysis of the Dye Marker,Solvent Blue 14, in Kerosene and Fuel Alcohol

The purpose of this paper is to develop an electroanalytical method based on square‐wave voltammetry (SWV) for the determination of the solvent blue 14 (SB‐14) in fuel samples. The electrochemical reduction of SB‐14 at glassy carbon electrode in a mixture of Britton‐Robinson buffer with N,N‐dimethylformamide (1 : 1, v/v) presented a well‐defined peak at?0.40 V vs. Ag/AgCl. All parameters of the SWV technique were optimized and the electroanalytical method presented a linear response from 1.0×10^?6 to 6.0×10^?6 mol L^?1 (r=0.998) with a detection limit of 2.90×10^?7 mol L^?1. The developed method was successfully utilized in the quantification of the dye SB‐14 in kerosene and alcohol samples with average recovery from 93.00 to 98.10%.     

Effects of magnetite nanoparticles on the thermorheological properties of carrageenan hydrogels

The influence of magnetite (Fe(3)O(4)) nanoparticles on the rheological properties of kappa-, iota- and lambda-carrageenan gels has been investigated. Small amplitude oscillatory shear measurements were performed to study the effect of the presence of Fe(3)O(4) nanoparticles with particle sizes of ca. 10 nm on the gel properties, as a function of carrageenan type, carrageenan concentration and magnetite load. The formation of Fe(3)O(4) nanoparticles on the presence of biopolymer was observed to promote the gelation process and lead to stronger gels as indicated by an increase in the gel viscoelastic moduli and of the gelation temperature. This effect was more marked for kappa-carrageenan than for iota- and lambda-carrageenan and has been proposed to depend not only on Fe(3)O(4) concentration but also on the concentration of potassium ions. A mechanism based on the combined effect of Fe(3)O(4) nanoparticles and potassium ions was suggested, involving the adsorption of potassium ions on the negatively charged surface of the Fe(3)O(4) nanoparticles, thus leading to an increase of the potassium ion concentration within the "carrageenan cages" containing the magnetite. This would, therefore, promote more extensive biopolymer helical aggregation, thus resulting in the formation of a stronger kappa-carrageenan gel in the presence of Fe(3)O(4), as observed. Since iota- and lambda-carrageenan gels are known to be less sensitive to potassium ions concentration, the effect of precipitating Fe(3)O(4) within these biopolymers is reduced.