Dynamical arrest, percolation, gelation, and glass formation in model nanoparticle dispersions with thermoreversible adhesive interactions

We report an experimental study of the dynamical arrest transition for a model system consisting of octadecyl coated silica suspended in n-tetradecane from dilute to concentrated conditions spanning the state diagram. The dispersion's interparticle potential is tuned by temperature affecting the brush conformation leading to a thermoreversible model system. The critical temperature for dynamical arrest, T*, is determined as a function of dispersion volume fraction by small-amplitude dynamic oscillatory shear rheology. We corroborate this transition temperature by measuring a power-law decay of the autocorrelation function and a loss of ergodicity via fiber-optic quasi-elastic light scattering. The structure at T* is measured using small-angle neutron scattering. The scattering intensity is fit to extract the interparticle pair-potential using the Ornstein-Zernike equation with the Percus-Yevick closure approximation, assuming a square-well interaction potential with a short-range interaction (1% of particle diameter). (1) The strength of attraction is characterized using the Baxter temperature (2) and mapped onto the adhesive hard sphere state diagram. The experiments show a continuous dynamical arrest transition line that follows the predicted dynamical percolation line until ? ≈ 0.41 where it subtends the predictions toward the mode coupling theory attractive-driven glass line. An alternative analysis of the phase transition through the reduced second virial coefficient B(2)* shows a change in the functional dependence of B(2)* on particle concentration around ? ≈ 0.36. We propose this signifies the location of a gel-to-glass transition. The results presented herein differ from those observed for depletion flocculated dispersion of micrometer-sized particles in polymer solutions, where dynamical arrest is a consequence of multicomponent phase separation, suggesting dynamical arrest is sensitive to the physical mechanism of attraction.     

Recombination in nonideal ion gas discharge afterglow plasma

Recombination rates in ion plasma are presented that are obtained by processing experimental data on gas discharge afterglow in fluorine and sulfur hexafluoride media. A theoretical explanation is given to the slowing down of the recombination rate of plasma in such media as the degree of Coulomb nonideality of the media increases. An additional factor for the suppression of recombination—solvation of ions—is considered. It is shown that, in the case of discharge afterglow plasma in a fluorine medium, the process of recombination proceeds in two stages with the formation of intermediate metastable ion pairs produced by ion-molecule clusters. In a sulfur hexafluoride medium, the formation of such pairs does not have a significant effect on the recombination rate.     

Imaging Local Proton Fluxes through a Polycarbonate Membrane by Using Scanning Electrochemical Microscopy and Functionalized Alkanethiols

A new application of scanning electrochemical microscopy (SECM) to probe the transport of protons through membranes is described. Herein, a probe ultramicroelectrode (UME) is modified with a self‐assembled monolayer (SAM) of 11‐mercaptoundecanoic acid to qualitatively image areas within different pH regions above a track‐etched membrane. The current response of the modified electrode in the presence of potassium hexacyanoferrate as electroactive component is different in acidic and alkaline solutions. Depending on the pH value of the solution, the SAM‐covered electrode exposes either a neutral or a negatively charged insulating monolayer at pH 3 or 7, respectively, which leads to an increase/decrease in the faradaic current due to electrostatic interactions between the neutral/charged surface and the charged redox mediator. Therefore, local pH changes in the close vicinity of a membrane‐like substrate lead to different current responses recorded at the tip electrode when scanning above the surface.     

Disposable Bismuth Oxide Screen Printed Electrodes for the High Throughput Screening of Heavy Metals

We present a simplified approach for the trace screening of toxic heavy metals utilizing bismuth oxide screen printed electrodes. The use of bismuth oxide instead of toxic mercury films facilitates the reliable sensing of lead(II), cadmium(II) and zinc(II). A linear range over 5 to 150 μg L^?1 with detection limits of 2.5 and 5 μg L^?1 are readily observed for cadmium and lead in 0.1 M HCl, respectively. Conducting a simultaneous multi‐elemental voltammetric detection of zinc, cadmium and lead in a higher pH medium (0.1 M sodium acetate solution) exhibited a linear range between 10 and 150 μg L^?1 with detection limits of 5, 10 and 30 μg L^?1 for cadmium, lead and zinc respectively. The sensor is greatly simplified over those recently reported such as bismuth nanoparticle modified electrodes and bismuth film coated screen printed electrodes. The scope of applications of this sensor with the inherent advances in electroanalysis coupled with the negliable toxicity of bismuth is extensive allowing high throughput electroanalysis.     

Screen printed electrodes provide micro-domain sites for fabricating disposable electro-catalytic ensembles

We demonstrate that bespoke screen printed electrodes which are basal plane-like in nature can be used as a template to produce randomly dispersed electro-catalytic micro-domains for analytical sensing purposes. Proof-of-concept is shown for the case of copper ensembles for nitrate detection and palladium ensembles for hydrazine sensing. The advantageous disposable nature of the ensemble precludes the need of pre-treatment between measurements. The screen printed ensembles act as excellent substrates for the deposition of a range of metals allowing the screen printed electrodes to act as a template for micro-domain ensembles of many different electrode materials for a variety of analytical challenges.     

Brief review related to the foundations of time-dependent density functional theory

The electron density n(r,t), which is the central tool of time-dependent density functional theory, is presently considered to be derivable from a one-body time-dependent potential V(r,t), via one-electron wave functions satisfying a time-dependent Schrödinger equation. This is here related via a generalized equation of motion to a Dirac density matrix now involving t. Linear response theory is then surveyed, with a special emphasis on the question of causality with respect to the density dependence of the potential. Extraction of V(r,t) for solvable models is also proposed.     

Production of high purity TeO2 single crystals for the study of neutrinoless double beta decay

High purity TeO₂ crystals are produced to be used for the search for the neutrinoless double beta decay of ¹³⁰Te. Dedicated production lines for raw material synthesis, crystal growth, and surface processing were built compliant with radio-purity constraints specific to rare event physics experiments. High sensitivity measurements of radio-isotope concentrations in raw materials, reactants, consumables, ancillaries, and intermediary products used for TeO₂ crystals production are reported. Indications are given on the crystals perfection and how it is achieved and maintained in a large scale production process. Production and certification protocols are presented and resulting ready-to-use TeO₂ crystals are described.     

Instantaneous quadrature components or Jones vector retrieval using the Pancharatnam-Berry phase in frequency domain low-coherence interferometry

We use the Pancharatnam-Berry phase as a multifunctional tool for low-coherence interferometry. This geometric phase shift enables instantaneous retrieval of the quadrature components of the complex interferometric signal. The phase shift is independent of wavelength and allows for a complex conjugate suppression of 40?dB for an optical bandwidth of 115?nm. Furthermore, this paper investigates the versatility of the geometric phase to perform polarization sensitive measurements. The Jones vector of the sample was obtained numerically, allowing sample birefringence and optical axis calculation.     

Tuning solute redox potentials by varying the anion component of room temperature ionic liquids

The electrode potentials for the two one electron oxidations of 1,2-diferrocenylethylene (bisferrocene, BF) were studied relative to that of the one electrode oxidation of decamethylferrocene in a variety of RTILs. The difference in these potentials was found to be very sensitive to the anion component of the ionic liquid showing the scope of these solutes as 'designer media' to tune the thermodynamic properties of solutes dissolved in them.     

Use of a polar-embedded stationary phase for the separation of tocopherols by CEC

A polar-embedded stationary phase (ULTIMA C18) has been investigated for the separation of alpha-, beta-, gamma- and delta-tocopherols by CEC in comparison with commercially available C(18) and C(30) n-alkyl RPs. The behavior of this stationary phase was tested for different mobile phases based on methanol, ACN, or mixtures thereof and different separation parameters such as retention factors and resolution were evaluated. The main feature of this stationary phase is the improved selectivity for the separation of beta- and gamma-tocopherols (positional isomers) when compared with the pure n-alkyl C(18) material, which was unable to resolve these compounds. Additionally, it is possible to observe a reversal in the elution order of the beta- and gamma-tocopherol isomers with respect to that obtained on the C(30) column. The resulting data indicate that the enhanced selectivity obtained with the polar-embedded stationary phase, with respect to the conventional C(18) material, is due to the participation of both hydrophobic and polar interactions: these latter are of the hydrogen bridge type with the amide group of the polar-embedded stationary phase, which increases the retention of the tocopherols and facilitates the discrimination between the beta- and gamma-isomers. Adequate separation of the four tocopherols was obtained by CEC using the polar-embedded stationary phase and 95:5 v/v methanol/water (5 mM Tris, final concentration) as the mobile phase.