Silver nanoparticles formed in bio- and chemical syntheses with biosurfactant as the stabilizing agent

In this work, the comparison of the physical properties of silver nanoparticles (AgNPs) obtained via the reduction of silver nitrate (AgNO₃) in biological and chemical (model) syntheses supplemented with the biosurfactant surfactin is described. In the studies, two strains of Bacillus subtilis (denoted T’1 and I’1a) were used. The biological synthesis of AgNPs was performed using supernatants obtained from cultures of bacteria growing on brewery effluents, molasses, and Luria–Bretani (LB) medium. In model experiments, ascorbic acid served as the reductant; surfactin acted as the stabilizing agent. The surfactin concentrations were adjusted to 5 and 30?mg/L, which corresponded to minimum and maximum surfactin concentrations as measured in the supernatants obtained from the B. subtilis cultures. The chemical synthesis was carried out at acidic as well as alkaline pH. Dynamic light scattering (DLS) revealed that in model and biological samples, single AgNPs were accompanied by aggregated structures. Transmission electron microscopy showed that the contribution of the aggregates in bacterial supernatants and in chemical synthesis is negligible under acidic conditions. However, in the alkaline environment, this contribution predominates. In the model experiments, smaller nanoparticles were formed with higher concentrations of surfactant. The presence of surfactin significantly increased the stability of AgNPs in both bio- and chemical syntheses.     

Solvent extraction of Cu,Mo, V,and U from leach solutions of copper ore and flotation tailings

A micro-cloud point extraction method was discussed for preconcentration and spectrophotometric quantification of U(VI). The method depends on complex formation between U(VI) and 2-(4-sulphophenyloazo)-1,8-dihydroxy-3,6-naphtalenedisulphonic acid (SPADNS) at pH 7.0 and subsequent extraction of the complex in a mixed surfactant medium (cethyltrimethyl ammonium bromide and Triton X-114). The separation was carried out in the presence of 1% Na₂SO₄ at room temperature. The calibration curve was linear up to 3000 µg L^?1. The enrichment factor, detection limit and precision were 16.0, 1.05 µg L^?1, and 2.3%, respectively. The method was employed for the determination of U(VI) in real samples with different matrices.     

Electrodeposition of gold nanoparticles at a solid|ionic liquid|aqueous electrolyte three-phase junction

Gold nanoparticles have been electrodeposited on an electrode through electrogeneration at an ITO|AuCl₄^? solution in an ionic liquid|aqueous electrolyte three-phase junction. The electrodeposition was carried out by inverted double-pulse potential chronoamperometry. The direct reduction of AuCl₄^? ions at the electrode is followed by a counterion transfer through the liquid|liquid interface. Contrary to the electrodeposition from a single ionic liquid phase, scanning electron microscopy reveals that the shape of the resulting nanoparticles is highly angular and well-developed with a diameter of 110 ± 30 nm. Catalytic oxidation of glucose on the modified electrode is demonstrated.     

Three dimensional film electrode prepared from oppositely charged carbon nanoparticles as efficient enzyme host

Three dimensional carbon film electrodes were prepared from oppositely charged carbon nanoparticles (ca. 9 to 18 nm diameter) by a layer-by-layer approach. This was done by alternative immersion of indium tin oxide plates into suspension of positively and negatively charged particles. A stable film is formed already after single immersion and withdrawal step as confirmed by scanning electron microscopy. Up to ten immersion and withdrawal steps can be used to systematically increase the amount of nanoparticulate carbon material. The capacitive current density and current density of hydrogen peroxide reduction are proportional to the number of immersion and withdrawal steps. The same can be seen for adsorbed redox active 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate). After adsorption of bilirubin oxidase into the film efficient bioelectrocatalytic dioxygen reduction is observed.     

Circular dichroism, optical rotation and absolute configuration of 2-cyclohexenone-cis-diol type phenol metabolites: redefining the role of substituents and 2-cyclohexenone conformation in electronic circular dichroism spectra

The absolute configurations of 2-cyclohexenone cis-diol metabolites resulting from the biotransformation of the corresponding phenols have been determined by comparison of their experimental and calculated circular dichroism spectra (TDDFT at the PCM/B2LYP/Aug-cc-pVTZ level), optical rotations (calculated at the PCM/B3LYP/Aug-cc-pVTZ level) and by stereochemical correlation. It is found that circular dichroism spectra and optical rotations of 2-cyclohexenone derivatives are strongly dependent on the ring conformation (M or P sofa S(5) or half-chair), enone non-planarity and the nature and positions of the hydroxy and alkyl substituents. The effect of non-planarity of the enone chromophore, including the distortion of the C=C bond, is determined for the model structures by TDDFT calculations at the PCM/B2LYP/6-311++G(2d,2p) level. Non-planarity of the C=C bond in the enone chromophore is commonly encountered in 2-cyclohexenone derivatives and it is a source of significant rotatory strength contribution to the electronic circular dichroism spectra. It is shown that the two lowest-energy transitions in acrolein and 2-cyclohexenone and its derivatives are n(C=O)-π(C=O)* and π(C=C)-π(C=O)*, as expected, while the shorter-wavelength (below 200 nm) transitions are of more complex nature. In 2-cyclohexenone and its alkyl derivatives it is predominantly a mixture of π(C=C)-π(C=C)* and π(C=C)-σ* transitions, whereas the presence of hydroxy substituent results in a dominant contribution due to the n(OH)-π(C=O)* transition. A generalized model for correlation of the CD spectra of 2-cyclohexenones with their structures is presented.     

Catalytic ignition of ionic liquids for propellant applications

In this proof of concept study, the ionic liquids, 2-hydroxyethylhydrazinium nitrate and 2-hydroxyethylhydrazinium dinitrate, ignited on contact with preheated Shell 405 (iridium supported on alumina) catalyst and energetically decomposed with no additional ignition source, suggesting a possible route to hydrazine replacements.     

Pulse shape analysis to reduce the background of BEGe detectors

A simple technique for pulse shape discrimination in HPGe-detectors of the so-called BEGe type, based on just one parameter obtained from one signal read out, is presented here. This technique allows discriminating between pulses generated when the deposited energy is located within a small region of about 1 mm³ from the pulses generated when the energy is deposited at different locations several mm or cm apart. Two possible applications using this technique are: (i) experiments that look for neutrinoless double β decay in ⁷⁶Ge, such as GERDA; (ii) γ spectrometry measurements where the Compton continuum can be reduced and the efficiency for cascading γ-rays can remain high. With this active background reduction technique a Compton suppression factor of about 3 was obtained. The detector response may be influenced by the detector size. The detector used for this study had a diameter of 6 cm, a thickness of 2.6 cm and a relative efficiency of 19%. The results obtained with this detector were consistent with the results obtained by Budjá? et al. [J Instrum 4:10, 2009] with a 50% relative efficiency BEGe detector.     

Ergodic properties of anomalous diffusion processes

In this paper we study ergodic properties of some classes of anomalous diffusion processes. Using the recently developed measure of dependence called the Correlation Cascade, we derive a generalization of the classical Khinchin theorem. This result allows us to determine ergodic properties of Lévy-driven stochastic processes. Moreover, we analyze the asymptotic behavior of two different fractional Ornstein–Uhlenbeck processes, both originating from subdiffusive dynamics. We show that only one of them is ergodic.     

Laser frequency stabilization by magnetically assisted rotation spectroscopy

We present a method of Doppler-free laser frequency stabilization based on magnetically assisted rotation spectroscopy (MARS) which combines the Doppler-free velocity-selective optical pumping (VSOP) and magnetic rotation spectroscopy. The stabilization is demonstrated for the atomic rubidium transitions at 780 nm. The proposed method is largely independent of stray magnetic fields and does not require any modulation of the laser frequency. Moreover, the discussed method allows one to choose between locking the laser exactly to the line center, or with a magnetically-controlled shift to an arbitrary frequency detuned by up to several natural linewidths. This feature is useful in many situations, e.g. for laser cooling experiments. In addition to presenting the principle of the method, its theoretical background and peculiarities inherent to the repopulation VSOP are discussed.     

Optical and microstructural properties of self-assembled InAs quantum structures in silicon

The InAs quantum structures were formed in silicon by sequential ion implantation and subsequent thermal annealing. Two kinds of crystalline InAs nanostructures were successfully synthesized: nanodots (NDs) and nanopyramids (NPs). The peaks at 215 and 235 cm^?1, corresponding to the transverse optical (TO) and longitudinal optical (LO) InAs single-phonon modes, respectively, are clearly visible in the Raman spectra. Moreover, the PL band at around 1.3 µm, due to light emission from InAs NDs with an average diameter 7±2 nm, was observed. The InAs NPs were found only in samples annealed for 20 ms at temperatures ranging from 1000 up to 1200°C. The crystallinity and pyramidal shape of InAs quantum structures were confirmed by HRTEM and XRD techniques. The average size of the NPs is 50 nm base and 50 nm height, and they are oriented parallel to the Si (001) planes. The lattice parameter of the NPs increases from 6.051 to 6.055 Å with the annealing temperature increasing from 1100 to 1200°C, due to lattice relaxation. Energy dispersive spectroscopy (EDS) shows almost stoichiometric composition of the InAs NPs.