Positronium interactions in liquids and porous substances

Positronium (Ps) is an important chemical probe for any given medium since it can interact with a variety of molecular electronic system to yield information, relevant to the understanding of underlying mechanistic processes, when subjected to the changes in physical parameters.In this article, its interaction is focused on two media that are important from the perspective of bio-chemical and technological studies, namely Ps-electron acceptor bound state formation in liquids (specially hydrogen bonding solvents) and also on a variety of porous material which are applicable in chemical/biochemical separations and other applications in technology. The underlying physical phenomenology in each case is separately dealt with giving suitable examples.     

Click chemistry in mesoporous materials: functionalization of porous silicon rugate filters

In this paper we report the use of the optical properties of porous silicon photonic crystals, combined with the chemical versatility of acetylene-terminated SAMs, to demonstrate the applicability of "click" chemistry to mesoporous materials. Cu(I)-catalyzed alkyne-azide cycloaddition reactions were employed to modify the internal pore surfaces through a two-step hydrosilylation/cycloaddition procedure. A positive outcome of this catalytic process, here performed in a spatially confined environment, was only observed in the presence of a ligand-stabilized Cu(I) species. Detailed characterization using Fourier transform infrared spectroscopy and optical reflectivity measurements demonstrated that the surface acetylenes had reacted in moderate to high yield to afford surfaces exposing chemical functionalities of interest. The porous silicon photonic crystals modified by the two-step strategy, and exposing oligoether moieties, displayed improved resistance toward the nonspecific adsorption of proteins as determined with fluorescently labeled bovine serum albumin. These results demonstrate that "click" immobilization offers a versatile, experimentally simple, and modular approach to produce functionalized porous silicon surfaces for applications as diverse as porous silicon-based sensing devices and implantable biomaterials.     

Electroosmosis in porous materials

Electroosmosis is the phenomenon of fluid flow induced by an applied electric field. This paper is concerned with electroosmosis in a porous material composed of closely-packed spheres immersed in a general electrolyte. A formula is obtained for the electroosmotic flow rate in the case when the double layer is much thinner than the particle radius. By combining this formula with electroosmosis measurements it is possible to determine the particle ζ potential. To test the validity of the model which underlies this, and most other electrokinetic calculations, ζ potentials obtained from Van der Put and Bijsterbosch's (J. Colloid Interface Sci. 92, 499, 1983) electroosmosis measurements are compared with potentials obtained from their conductivity and electrophoresis measurements.     

Positronium lifetime in polymers

A model describing the relationship between the orthopositronium lifetime and the volume of a void, located in a synthetic zeolite, is analyzed. Our idea, which allows us to take into account the effects of temperature, comprises the introduction of a non-Hermitian term in the Hamiltonian, which accounts for the annihilation of the orthopositronium. The predictions of the present model are also confronted against an already known experimental result.     

Surface chemistry of porous magnesium fluoride

Porous preparations of magnesium fluoride were obtained from magnesium sulphate and magnesium carbonate and their surface properties have been studied. It has been shown that pure magnesium fluoride has a weak surface acidity of the Lewis type and no protonic sites stronger than H_R?0.82. Base properties of MgF₂ surfaces are more pronounced than acid ones, but the base strength is low. Surfaces of MgF₂ also bear oxidizing and reducing centres capable of forming ion radicals with adsorbed perylene and tetracyanoethylene. The low catalytic activity of magnesium fluoride for acid catalysed reactions suggests the application of MgF₂ as a catalyst support rather than as a catalyst.     

High-pressure chemistry of nitride-based materials

Besides temperature at one atmosphere, the applied pressure is another important parameter for influencing and controlling reaction pathways and final reaction products. This is relevant not only for the genesis of natural minerals, but also for synthetic chemical products and technological materials. The present critical review (316 references) highlights recent developments that utilise high pressures and high-temperatures for the synthesis of new materials with unique properties, such as high hardness, or interesting magnetic or optoelectronic features. Novel metal nitrides, oxonitrides as well as the new class of nitride-diazenide compounds, all formed under high-pressure conditions, are highlighted. Pure oxides and carbides are not considered here. Moreover, syntheses under high-pressure conditions require special equipment and preparation techniques, completely different from those used for conventional synthetic approaches at ambient pressure. Therefore, we also summarize the high-pressure techniques used for the synthesis of new materials on a laboratory scale. In particular, our attention is focused on reactive gas pressure devices with pressures between 1.2 and 600 MPa, multi-anvil apparatus at P < 25 GPa and the diamond anvil cell, which allows work at pressures of 100 GPa and higher. For example, some of these techniques have been successfully upgraded to an industrial scale for the synthesis of diamond and cubic boron nitride.     

Positronium interactions in organic solvents

In the present work, the chemistry of the positronium (Ps) species has been investigated in pure benzene, pyridine and their mixtures with pyridine concentrations at 4.12, 6.18 and 8.24 M, respectively, using the Doppler-broadened line-shape analysis technique. It is seen that the intensities of the para-(p-Ps) and ortho-Ps (o-Ps) in benzene and that of p-Ps in pyridine follow the Ore-model predictions while the intensity of o-Ps in pyridine is much lower than expected from this model. On the basis of these observations and of decrease in the o-Ps lifetime with increasing pyridine concentration in various organic solvents as reported in literature, it is concluded that pick-off is not the only quenching mechanism for Ps in organic solvents and pyridine is a quencher of Ps-species rather than an inhibitor. Calculations carried out considering a diffusion-controlled mechanism of Ps-quenching in pyridine via unstable (dissociative) complex/adduct formation and the bubble model show that the quenching rate is diffusion controlled and the pick-off rate is in accordance with the free-volume model. These conclusions were confirmed in the mixtures of benzene and pyridine.     

PEGylation of porous silicon using click chemistry

Porous silicon has received considerable interest in recent years in a range of biomedical applications, with its performance determined by surface chemistry. In this work, we investigate the PEGylation of porous silicon wafers using click chemistry. The porous silicon wafer surface chemistry was monitored at each stage of the reaction via photoacoustic Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, whereas sessile drop contact angle and model protein adsorption measurements were used to characterize the final PEGylated surface. This work highlights the simplicity of click-chemistry-based functionalization in tailoring the porous silicon surface chemistry and controlling protein-porous silicon interactions.     

Applications of self-assembled monolayers in materials chemistry

Self-assembly provides a simple route to organise suitable organic molecules on noble metal and selected nanocluster surfaces by using monolayers of long chain organic molecules with various functionalities like -SH,-COOH,-NH₂, silanes etc. These surfaces can be effectively used to build-up interesting nano level architectures. Flexibility with respect to the terminal functionalities of the organic molecules allows the control of the hydrophobicity or hydrophilicity of metal surface, while the selection of length scale can be used to tune the distant-dependent electron transfer behaviour. Organo-inorganic materials tailored in this fashion are extremely important in nanotechnology to construct nanoelctronic devices, sensor arrays, supercapacitors, catalysts, rechargeable power sources etc. by virtue of their size and shape-dependent electrical, optical or magnetic properties. The interesting applications of monolayers and monolayer-protected clusters in materials chemistry are discussed using recent examples of size and shape control of the properties of several metallic and semiconducting nanoparticles. The potential benefits of using these nanostructured systems for molecular electronic components are illustrated using Au and Ag nanoclusters with suitable bifunctional SAMs.     

Capillary condensation of adsorbates in porous materials

Hysteresis in capillary condensation is important for the fundamental study and application of porous materials, and yet experiments on porous materials are sometimes difficult to interpret because of the many interactions and complex solid structures involved in the condensation and evaporation processes. Here we make an overview of the significant progress in understanding capillary condensation and hysteresis phenomena in mesopores that have followed from experiment and simulation applied to highly ordered mesoporous materials such as MCM-41 and SBA-15 over the last few decades.     

Time-dependent diffusion coefficients in periodic porous materials

We derive an approximate solution for the Laplace transform of the time-dependent diffusion coefficient, D(t), of a molecule diffusing in a periodic porous material. In our model, the material is represented by a simple cubic lattice of identical cubic cavities filled with a solvent and connected by small circular apertures in otherwise reflecting cavity walls, the thickness of which can be neglected. The solution describes the decrease of D(t) from its initial value, D(0) = D, where D is the diffusion constant in the free solvent, to its asymptotic value, D(infinity) = D(eff), which is much smaller than D. A simple heuristic formula for the mean-squared displacement of the diffusing molecule is suggested. The theoretically predicted results are in good agreement with the data obtained from Brownian dynamics simulations.     

Diffusion of ions in unsaturated porous materials

In a salinity gradient, the diffusion of ions through the connected porosity of a porous and charged material is influenced by the charged nature of the interface between the pore water and the solid. This influence is exerted through the generation of a macroscopic electrical field termed the diffusion or membrane potential. This electrical field depends on the excess of counterions located in the pore space counterbalancing the charge density of the surface of the solid. In unsaturated porous materials, we have to consider (1) the effect of the charged nature of the air/water interface, (2) the increase of the counterion density as the counterions are packed in a smaller volume when the saturation of the nonwetting phase (air) increases, and (3) the influence of the water saturation upon the tortuosity of the water phase. The volume average of the Nernst-Planck equation is used to determine the constitutive equations for the coupled diffusion flux and current density of a multicomponent electrolyte in unsaturated conditions. We assume that water is the wetting phase for the solid phase. We neglect the electro-osmotic flow in the coupled constitutive equations and the deformation of the medium (the medium is assumed to be both isotropic and rigid). This model explains well the observed tendency of strong decreases of the apparent diffusion coefficient of ions with the decrease of the saturation of the water phase under steady-state conditions. This decrease is mainly due to the influence of the saturation upon the tortuosity of the water phase.     

Positronium annihilation in amine-cured epoxy polymers

Positronium annihilation spectroscopy (PAS) has been used to study the microstructural properties of amine-cured epoxy polymers. We have determined the free-volume “hole” sizes in these polymers by comparing the observed ortho-positronium lifetimes with the known lifetime–free volume correlation for low-molecular-weight systems. The free volumes for four epoxies with different crosslink densities are found to vary significantly over the temperature range between ?78° and 250°C. The free-volume holes for these polymers are found to range from 0.025 to 0.220 nm³. Two important transition temperatures were found: one corresponds to the glass transition temperature T_g determined by differential scanning calorimetry (DSC), and the other occurs about 80–130°C below T_g. The sub-T_g transition temperature is interpreted tentatively as being where hole size reaches dimensions adequate for positronium trapping or else the onset temperature for local mode or side-chain motions. These two transition temperatures plus two additional onset temperatures are found to be correlated with crosslink densities calculated from stoichiometry.     

Positronium in solid phases of phenanthrene

Temperature dependence of positronium formation in phenanthrene was investigated. On crossing the solid-solid phase transition point in both directions a sharp decrease of positronium creation probability was observed. The effect is discussed in terms of formation of an unstable phase, and of possible pyroelectricity of phenanthrene.     

The role of reference materials in analytical chemistry

The paper demonstrates a concept and possible models for an international infrastructure of chemical measurements by using reference materials.The function of reference materials to establish traceability and means of quality assurance is emphasized.